Solid polymer electrolytes for all-solid-state batteries

Abstract

The present technology relates to a solid polymer electrolyte film comprising a heterogeneous mixture of at least two different polymers, one of which is a branched polyether having at least three branches. Their manufacturing process, as well as electrochemical cells, batteries, and electrochemical storage cells comprising them, and their uses are also described. According to a first aspect, the present technology relates to a solid electrolyte comprising a first polymer, a second polymer, optionally a plasticizer, and optionally an ionic organic additive, wherein the first polymer is a branched polyether having at least three branches, and the first polymer and the second polymer are different and form a heterogeneous mixture.

Description

[Technical Field]

[0001] Related Applications This application claims priority under applicable law to Canadian Patent Application No. 3,193,279, filed March 17, 2023, the contents of which are incorporated herein by reference in their entirety for all purposes.

[0002] Technical Field The present technology relates to solid polymer electrolyte films, processes for their manufacture, and electrochemical cells and batteries comprising them. [Background technology]

[0003] background The liquid electrolytes used in lithium-ion batteries are flammable and gradually degrade, forming a passivation layer on the surface of the lithium film or solid electrolyte interface (SEI) that irreversibly consumes lithium, thereby reducing the battery's coulombic efficiency. Furthermore, the lithium anode undergoes significant morphological changes during battery cycling, resulting in the formation of lithium dendrites. These typically migrate through the electrolyte, which can eventually cause a short circuit.

[0004] Safety concerns and the need for higher energy density have prompted research into the development of all-solid-state rechargeable lithium batteries using polymer or ceramic electrolytes (both of which are more stable with respect to metallic lithium and reduce the growth of lithium dendrites). However, the use of such solid electrolytes results in several drawbacks, such as loss of reactivity or ionic conductivity, and poor contact between solid interfaces.

[0005] Therefore, there is a constant need to develop new solid electrolyte films for use in all-solid-state batteries. Summary of the Invention [Means for solving the problem]

[0006] overview According to a first aspect, the present technology relates to a solid electrolyte comprising a first polymer, a second polymer, optionally a plasticizer, and optionally an ionic organic additive, wherein the first polymer is a branched polyether having at least three branches, and the first polymer and the second polymer are different and form a heterogeneous mixture.

[0007] In one embodiment, the first polymer is a branched polyether having at least four branches in a star configuration. According to another embodiment, the branches of the first polymer comprise polymer chains of alkylene oxide units, preferably the alkylene oxide units comprise ethylene oxide units, propylene oxide units, or a combination of ethylene oxide and propylene oxide units.

[0008] In another embodiment, the first polymer is crosslinkable and comprises crosslinkable groups, e.g., located on side chains or as terminal groups at the ends of branches, preferably as terminal groups at the ends of branches. According to yet another embodiment, the first polymer is further crosslinked, and the polymer is the product of crosslinking of the crosslinkable groups, e.g., located on side chains or as terminal groups at the ends of branches, preferably as terminal groups at the ends of branches of the first polymer. According to either of the foregoing embodiments, the crosslinkable groups can be selected from vinyl groups, acrylate groups, methacrylate groups, glycidyl groups, and mercapto groups, and combinations of at least two of these.

[0009] According to one embodiment, the first polymer has a number average molecular weight of 5 to 5 million, or 5,000 to 1,000,000, or 20,000 to 500,000. According to another embodiment, the first polymer is present in the solid electrolyte at a concentration of about 5% to about 80% by weight, about 5% to about 60% by weight, about 5% to about 35% by weight, about 10% to about 30% by weight, or about 12% to about 25% by weight.

[0010] According to another embodiment, the second polymer comprises substituted polyethylene chains. In one embodiment, the second polymer comprises a group selected from fluorine, an optionally fluorinated alkyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocycloalkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a polyether group, an optionally fluorinated alkyl ester group, a polyether ester group, or a combination of two or more thereof.

[0011] In another embodiment, the second polymer comprises a copolymer, preferably a copolymer comprising units comprising groups selected from fluorine, optionally fluorinated alkyl groups, optionally fluorinated alkyl ester groups, polyether ester groups, or combinations of two or more of these, and optionally units comprising optionally substituted aryl and / or carboxylic acid groups.

[0012] According to one embodiment, the second polymer comprises a random copolymer or a block copolymer, or a combination of random and block copolymers, for example, the second polymer comprises a block copolymer comprising at least two blocks of different monomers, and at least one of the two blocks comprises a random copolymer sequence.

[0013] According to yet another embodiment, the second polymer comprises at least one monomer derived from the polymerization of poly(ethylene glycol) methyl ether (meth)acrylate, (meth)acrylic acid, 1,1-difluorovinyl, tetrafluorovinyl, hexafluoropropene, 2,2,2-trifluoroethyl (meth)acrylate, styrene, divinylbenzene, or a combination of two or more thereof; preferably, the second polymer comprises at least one monomer derived from the polymerization of poly(ethylene glycol) methyl ether (meth)acrylate (PEGMA), 1,1-difluorovinyl (PVDF), tetrafluorovinyl (PTFE), hexafluoropropene (HFP), 2,2,2-trifluoroethyl (meth)acrylate, or a combination of two or more thereof, and, optionally, monomers derived from the polymerization of (meth)acrylic acid, styrene, and / or divinylbenzene.

[0014] In one embodiment, the second polymer comprises a polymer selected from poly[styrene-b-poly(poly(ethylene glycol) methyl ether methacrylate-co-methacrylic acid)] (PS-bP(PEGMA-co-MAA), poly[poly(styrene-co-divinylbenzene)-b-poly(poly(ethylene glycol) methyl ether methacrylate-co-methacrylic acid)] (P(S-co-DVB)-bP(PEGMA-co-MAA), poly(vinylidene fluoride)-co-hexafluoropropylene, and poly[(2,2,2-trifluoroethyl methacrylate)-co-(poly(ethylene glycol) methyl ether methacrylate)]], or a combination of at least two thereof. In embodiments, the second polymer comprises poly[styrene-b-poly(poly(ethylene glycol) methyl ether methacrylate-co-methacrylic acid)] (PS-bP(PEGMA-co-MAA), poly[poly(styrene-co-divinylbenzene)-b-poly(poly(ethylene glycol) methyl ether methacrylate-co-methacrylic acid)] (P(S-co-DVB)-bP(PEGMA-co-MAA), or a combination thereof, or the second polymer comprises poly(vinylidene fluoride)-co-hexafluoropropylene, poly[(2,2,2-trifluoroethyl methacrylate)-co-(poly(ethylene glycol) methyl ether methacrylate), or a combination thereof.

[0015] According to one embodiment, the second polymer is a mixture of at least two polymers as defined above, e.g., a mixture of at least two polymers including at least poly(vinylidene fluoride)-co-hexafluoropropylene. According to another embodiment, the second polymer has a number average molecular weight of 5 to 5 million, or 5,000 to 1,000,000, or 20,000 to 500,000. In another embodiment, the second polymer is in the form of particles (e.g., microparticles, nanoparticles, picoparticles, or mixtures comprising two or more thereof), such as powders, fibers, rods, vesicles, micelles, etc. In another embodiment, the second polymer is present in the solid electrolyte at a concentration of about 3 wt % to about 40 wt %, about 4 wt % to about 30 wt %, about 4 wt % to about 25 wt %, about 8 wt % to about 20 wt %, or about 10 wt % to about 18 wt %.

[0016] In another embodiment, the solid electrolyte further comprises a third polymer different from the first polymer and the second polymer. According to one embodiment, the third polymer is an optionally substituted, preferably phosphorus-containing polysaccharide (such as cellulose fiber), or a combination thereof.

[0017] According to one embodiment, the ionic organic additive is preferably present in the solid electrolyte at a concentration of from about 0.5% to about 35% by weight, or from about 2% to about 30% by weight, or from about 5% to about 20% by weight.

[0018] In another embodiment, the ionic organic additive is represented by Formula I or II: [ka] [In the formula, A - is a delocalized anion, R + -N + (R1R2R3) and -P + (R1R2R3) group, 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 form a heterocycle having one or more rings and 3 to 12 members, and R3 is as defined above, or R1, R2, and R3 together with the nitrogen or phosphorus atom form a heteroaromatic or partially unsaturated heterocycle 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. is a bifunctional ionic molecule.

[0019] According to one embodiment, the delocalized anion is a hexafluorophosphate ion (PF6 - ), bis(trifluoromethanesulfonyl)imide ion (TFSI - ), bis(fluorosulfonyl)imide ion (FSI - ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide ion (FTFSI - ), 2-trifluoromethyl-4,5-dicyanoimidazol- ate ion (TDI - ), 4,5-dicyano-1,2,3-triazolate ion (DCTA - ), bis(pentafluoroethylsulfonyl)imide ion (BETI - ), difluorophosphate ion (DFP - ), tetrafluoroborate ion (BF4 - ), bis(oxalato)borate ion (BOB - ), nitrate ions (NO3 - ), perchlorate ion (ClO4 - ), hexafluoroarsenate ion (AsF6 - ), trifluoromethanesulfonate ion (CF3SO3 - or- OTf), fluoroalkyl phosphate ion ([PF3(CF2CF3)3] - or FAP - ), tetrakis(trifluoroacetoxy)borate ion ([B(OCOCF3)4] - or TFAB - ), bis(1,2-benzenediolato(2-)-O,O')borate ion ([B(C6O2)2] - or BBB - ), difluoro(oxalato)borate ion (BF2(C2O4) - or FOB - ), and the formula BF2O4R x (R x =C 2~4 alkyl), preferably hexafluorophosphate (PF6 - ), bis(trifluoromethanesulfonyl)imide ion (TFSI - ), bis(fluorosulfonyl)imide ion (FSI - ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide ion (FTFSI - ), tetrafluoroborate ion (BF4 - ), and trifluoromethanesulfonate ion (CF3SO3 - or - OTf), more preferably bis(trifluoromethanesulfonyl)imide ion (TFSI - )

[0020] According to another embodiment, R + -N + (R1R2R3) groups. In one embodiment, R1, R2, and R3 are independently substituted or unsubstituted linear or branched C 1~12 In another embodiment, R1, R2, and R3 are independently selected from linear or branched C alkyl groups. 1~12In yet another embodiment, 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 defined in claim 25, preferably R3 is selected from the group consisting of C 1~12 Alkyl, or C 1~4 According to another alternative, R1, R2, and R3 together with the nitrogen atom form a heteroaromatic or partially unsaturated heterocycle having one or more rings and 5 to 12 members. According to some embodiments, R + teeth, [ka] wherein R3 is as defined in claim 25 and R4 is a substituted or unsubstituted linear or branched C 1~12 Alkyl group, C 1~12 Alkenyl group, or C 1~12 alkynyl group, and R5 is a hydrogen atom or a substituted or unsubstituted straight-chain or branched C 1~12 Alkyl group, C 1~12 Alkenyl group or C 1~12 an alkynyl group, and the heterocycle is optionally substituted] is selected from.

[0021] According to one embodiment, R4 is C 1~4 According to another embodiment, R5 is C 1~4 According to yet another embodiment, R3 is an unsubstituted C 1~4 It is an alkyl group, for example, preferably selected from methyl, ethyl, n-propyl or i-propyl, and n-butyl, i-butyl, s-butyl or t-butyl groups.

[0022] In some embodiments, R + -P+ (R1R2R3) groups. In one embodiment, R1, R2, and R3 are independently substituted or unsubstituted linear or branched C 1~12 In another embodiment, R1, R2, and R3 are independently selected from linear or branched C alkyl groups. 1~12 alkyl groups, or at least one of R1, R2, or R3 is substituted with a halogen atom, or an alkoxy group, an ether group, an ester group, or a siloxy group.

[0023] In one embodiment, n in Formulas I and II is a number ranging from 2 to 10, or from 3 to 8, or from 4 to 6.

[0024] In another embodiment, the ionic bifunctional molecule is 1,1'-(1,6-hexamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide, or 1,1'-(1,12-dodecamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide, or 1,1'-(2,2'-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide, or 1,1'-(thiolbis(1,2-ethane))bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide, or 3,3'-(1,6-hexamethylene)bis(1,2-dimethylimidazolium)bis(trifluoromethanesulfonyl)imide.

[0025] According to another embodiment, the plasticizer is present in the solid electrolyte at a concentration of preferably about 5% to about 50% by weight, or about 10% to about 40% by weight, or about 20% to about 30% by weight. In one embodiment, the plasticizer is selected from types of liquids such as glycol diethers (e.g., tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, and ionic liquids, preferably glycol diether-type liquids (e.g., TEGDME).

[0026] According to yet another embodiment, the solid electrolyte further comprises an alkali metal salt, preferably a lithium salt, preferably at a concentration of about 5% to about 40% by weight, or about 15% to about 40% by weight, or about 20% to about 35% by weight in the solid electrolyte. In one embodiment, the salt comprises a cation of an alkali metal (preferably Li) and a hexafluorophosphate ion (PF6 - ), bis(trifluoromethanesulfonyl)imide ion (TFSI - ), bis(fluorosulfonyl)imide ion (FSI - ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide ion ((FSI)(TFSI) - ), 2-trifluoromethyl-4,5-dicyanoimidazol- ate ion (TDI - ), 4,5-dicyano-1,2,3-triazolate ion (DCTA - ), bis(pentafluoroethylsulfonyl)imide ion (BETI - ), difluorophosphate ion (DFP - ), tetrafluoroborate ion (BF4 - ), bis(oxalato)borate ion (BOB - ), nitrate ions (NO3 - ), chloride ions (Cl - ), bromide ion (Br - ), fluoride ion (F - ), perchlorate ion (ClO4 - ), hexafluoroarsenate ion (AsF6 - ), trifluoromethanesulfonate ion (SO3CF3 - )(Tf - ), fluoroalkyl phosphate ion [PF3(CF2CF3)3 - ](FAP - ), tetrakis(trifluoroacetoxy)borate ion [B(OCOCF3)4] - (TFAB - ), bis(1,2-benzenediolato(2-)-O,O')borate ion [B(C6O2)2] - (B.B.B. - ), difluoro(oxalato)borate ion (BF2(C2O4)- )(FOB - ), formula BF2O4R x - (In the formula, R x =C 2~4 and an anion selected from the group consisting of anions of (alkyl), any combination thereof, for example, LiTFSI or LiFSI.

[0027] 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 defined herein.

[0028] According to one embodiment, the positive electrode comprises a positive electrode material including a positive electrode electrochemically active material, preferably on a current collector.

[0029] In one embodiment, the positive electrode electrochemically active material is selected from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides. In another embodiment, the positive electrode electrochemically active material is selected from LiM'PO4 (where M' is Fe, Ni, Mn, Co, or a combination of at least two of these), LiVO, VOF, LiVO, LiMnO, Li 1+w M''O 2-a X b (M'' is Mn, Co, Ni, Mg, Al, Zr, W, Ti, Nb, V, Fe, Mo, or a combination thereof (NMC, Li 1+w Mn x Co y Ni z O2, etc.), and X is F, S, or a combination thereof), Li 1+w (NiM''')O2 (M''' is Mn, Co, Mg, Al, W, Fe, Cr, Ti, Zr, Nb, Mo, V, or a combination thereof), elemental sulfur, selenium or iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, a carbon-based active material such as graphite, an organic cathode active material, or a combination of two or more of these when compatible with each other.

[0030] According to another embodiment, the positive electrode material further comprises an electronically conductive material, a binder, a salt, an ionic organic additive, and / or inorganic particles.

[0031] In another embodiment, the negative electrode comprises a negative electrode material including a negative electrode electrochemically active material, preferably the negative electrode material being on a current collector.

[0032] According to one embodiment, the negative electrode electrochemically active material comprises a metal film comprising an alkali metal selected from an alkali metal or alkaline earth metal, or an alloy comprising an alkali metal or alkaline earth metal, for example, lithium and sodium, or an alloy comprising lithium or sodium, preferably lithium, or an alloy comprising lithium.

[0033] In alternative embodiments, the negative electrode electrochemically active material may be selected from the group consisting of intermetallic compounds (e.g., SnSb, TiSnSb, CuSb, AlSb, FeSb, FeSn, and CoSn), metal oxides, metal nitrides, metal phosphides, metal phosphates (e.g., LiTi(PO)), 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 suitable. In one embodiment, the metal oxide is of the formula M"" b O cCompounds of M''''' (where M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof, and b and c are numbers such that the c:b ratio is in the range of 2 to 3) (e.g., MoO3, MoO2, MoS2, V2O5, and TiNb2O7), spinel oxides (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4), and LiM'''''O (where M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof) (e.g., lithium titanate (Li4Ti5O 12 ) or lithium and molybdenum oxide (Li2Mo4O 13 etc.)) are selected.

[0034] According to another embodiment, the negative electrode material further comprises an electronically conductive material, a binder, a salt, an ionic organic additive, and / or inorganic particles.

[0035] According to another aspect, the present technology also relates to a battery comprising at least one electrochemical cell as defined herein. According to 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, and is preferably a lithium battery or a lithium ion battery. [Brief explanation of the drawings]

[0036] [Figure 1] FIG. 1 shows a transmission electron microscope (TEM) image of PS-NP-2 nanoparticles prepared according to Example 1(c).

[0037] [Figure 2] FIG. 2 shows the normalized heat flux curve versus temperature for Film 6 prepared in Example 1(f) compared to films of PVDF-HFP and PVDF-HFP / additive blends.

[0038] [Figure 3] FIG. 3 shows a graph of Young's modulus for Film 6 membrane prepared in Example 1(f).

[0039] [Figure 4] FIG. 4 shows the ionic conductivities of symmetric cells 1-4 measured as in Example 3(b).

[0040] [Figure 5] FIG. 5 shows the discharge capacity results as a function of cycle number for complete batteries 1-9 containing films 2-10, respectively, when cycled as described in Example 3(d). DETAILED DESCRIPTION OF THE INVENTION

[0041] Detailed Description All technical and scientific terms and expressions used herein have the same definitions as commonly understood by those skilled in the art. However, the definitions of some of the terms and expressions used are set forth below.

[0042] When the term "about" is used herein, it means approximately, in the region of, or in the vicinity. For example, when the term "about" is used in connection with a numerical value, it modifies the numerical value up or down by 10% from its nominal value. This term may also take into account, for example, experimental error or rounding of measuring devices.

[0043] When a range of values ​​is referred to in this application, the lower and upper limits of the range are always included in the definition unless otherwise specified. When a range of values ​​is referred to in this application, all intermediate ranges and subranges are also included in the definition, as well as the individual values ​​included in the range of values.

[0044] In this application, when the article "a" is used to introduce an element, it does not mean "only one," but rather "one or more." It should be understood that if the description states that a particular step, component, element, or function "may" be included or "might" be included, this particular step, component, element, or function need not be included in every embodiment.

[0045] The chemical structures set forth herein are drawn according to the conventions of the art, and where an atom, such as a carbon atom as depicted, appears to have incomplete valences, it is assumed that the valences are satisfied by one or more hydrogen atoms, even if they are not explicitly drawn.

[0046] As used herein, the term "alkyl" refers to an optionally substituted saturated hydrocarbon group having 1 to 12 carbon atoms (unless otherwise indicated), including straight-chain or branched alkyl groups, preferably 1 to 6 carbon atoms. Non-limiting examples of alkyl can include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, isopropyl, tert-butyl, sec-butyl, isobutyl, and the like. Similarly, an "alkylene" group refers to an alkyl group positioned between groups, e.g., methylene, ethylene, propylene, butylene, etc. "C m ~C n Alkyl" and "C m ~C n The term "alkylene" refers to an alkyl or alkylene group, respectively, having from the designated number "m" to the designated number "n" of carbon atoms.

[0047] As used herein, the term "cycloalkyl" refers to a group containing one or more saturated or partially unsaturated (non-aromatic) carbocyclic rings containing 3 to 15 members in a monocyclic or polycyclic ring system, including spiro (sharing one atom), fused (sharing at least one bond), or bridged carbocyclic rings, and 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, cycloheptyl, and the like. When a cycloalkyl group is located between two functional groups, the term cycloalkylene may also be used. "C m ~C n cycloalkyl" and "C m ~C n The term "cycloalkylene" refers to a cycloalkyl or cycloalkylene group, respectively, having from the designated number "m" to the designated number "n" of carbon atoms.

[0048] As used herein, the term "heterocycloalkyl" refers to a group containing a saturated or partially unsaturated (non-aromatic) carbocyclic ring containing 3 to 15 members in a monocyclic or polycyclic system, including spiro (sharing one atom), fused (sharing at least one bond), or bridged carbocyclic rings, which may be optionally substituted, and which contain carbon atoms and 1 to 4 heteroatoms (e.g., N, O, S, or P) or groups containing such heteroatoms (e.g., NH, NR x (R xThe heterocycloalkyl group may be an alkyl, acyl, aryl, heteroaryl, or cycloalkyl group, PO2, SO2, SO2, and other similar groups. The heterocycloalkyl group may be linked to a carbon atom or a heteroatom (e.g., via a nitrogen atom) if possible. The term heterocycloalkyl includes both unsubstituted and substituted heterocycloalkyl groups. When a heterocycloalkyl group is located between two functional groups, the term heterocycloalkylene may also be used. "C m ~C n Heterocycloalkyl" and "C m ~C n The term "heterocycloalkylene" refers to a heterocycloalkyl or heterocycloalkylene group, respectively, having from the indicated number "m" to the indicated number "n" ring atoms, including carbon atoms and heteroatoms.

[0049] As used herein, the term "aromatic" or "aryl" refers to an aromatic group having 4n+2 conjugated π (pi) electrons, where n is a number from 1 to 3, in a monocyclic group or a fused bicyclic or tricyclic system (at least one of the rings in the system is aromatic) with a total of 6 to 15 ring members. The term "aryl" or "aromatic" refers to both monocyclic and conjugated 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, perylenyl, and the like. "C m ~C n aryl" and "C m ~C n The term "arylene" refers to an aryl or arylene group, respectively, having from the indicated number "m" to the indicated number "n" of carbon atoms.

[0050] The terms "heteroaromatic" or "heteroaryl" refer to heteroaromatic rings having, for example, 5 to 18 ring atoms, preferably 5, 6, or 9 ring atoms, and which, in addition to carbon atoms, contain 1 to 5 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 4n+2 conjugated π (pi) electrons, where n is a number from 1 to 3, with a C1-C3 alkyl group (which may be 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 linked by a C1-C3 alkyl group (also called heteroarylalkyl or heteroaralkyl). Heteroaryl groups may be linked through a carbon atom of the ring or to a heteroatom (e.g., via a nitrogen atom) where possible. "C m ~C n Heteroaryl" and "C m ~C n The term "heteroarylene" refers to a heteroaryl or heteroarylene group, respectively, having from the indicated number "m" to the indicated number "n" ring atoms, including carbon atoms and heteroatoms.

[0051] Generally, the term "substituted" means that one or more hydrogen atoms on the specified group are replaced with a suitable substituent. The substituents or combinations of substituents contemplated herein are those that result in the formation of a chemically stable compound. Examples of substituents include halogen atoms (such as fluorine), and hydroxyl, oxo, alkyl, alkoxy, alkoxyalkyl, nitrile, azide, carboxylate, alkoxycarbonyl, alkylcarbonyl, primary, secondary, or tertiary amine, amide, nitro, silane, siloxane, thiocarboxylate, sulfonyl, sulfonate, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycloalkyl, or combinations thereof.

[0052] As used herein, the terms "monomer," "monomer unit," and "unit" refer to a molecule that can undergo polymerization or the same molecule that is present in the resulting polymer or polymer chain.

[0053] As used herein, the term "polymerization" refers to the process of converting a monomer or mixture of monomers into a polymer, the structure of which essentially comprises multiple repeating units derived from the monomer.

[0054] The term "polymer" means a macromolecule that includes multiple repeating units or patterns derived from one or more monomers and / or macromonomers. Similarly, a "polymer chain" refers to the polymeric portion of a polymer, e.g., the backbone or branches of the polymer.

[0055] The phrase "crosslinkable functional group" or "crosslinkable group" of a polymer refers to a group having at least one functional group that can react to form crosslinks between the backbone and / or branches of the polymer, thereby forming a three-dimensional network.

[0056] The terms "(meth)acrylate" or "(meth)acrylic" designate an acrylate or acrylic group, i.e., an acrylate group, a methacrylate group, an acrylic group, or a methacrylic group, with or without a methyl substituted group.

[0057] In the context of this document, "inclusive between x and y" or "x to y" means a range that includes the limits x and y, unless otherwise indicated. For example, the range "inclusive between 1 and 50" also includes the values ​​1 and 50.

[0058] This document describes electrolyte compositions specifically intended for the production of solid polymer electrolytes, for example in the form of a film. These solid electrolytes comprise at least a first polymer and a second polymer, and optionally a plasticizer and / or an ionic organic additive, where the first polymer and the second polymer are different and form a heterogeneous mixture. It is understood that the first polymer or the second polymer may comprise a mixture of polymers, and more specifically, the second polymer may comprise a mixture of two polymers as described herein. In a preferred embodiment, the solid electrolyte does not include inorganic particles, such as ceramics or glass ceramics.

[0059] The first polymer is generally a branched polymer, preferably a polyether, having at least three branches. For example, the first polymer may be a branched polyether having at least four branches, for example, in a star configuration. In some cases, the arms of the first polymer comprise polymer chains of alkylene oxide units, preferably ethylene oxide units, propylene oxide units, or a combination of ethylene oxide units and propylene oxide units.

[0060] In some examples, the first polymer is crosslinkable, for example, comprising crosslinkable groups located on side chains or as branch end terminal groups, preferably as branch end terminal groups. In other examples, the first polymer is crosslinked, and the polymer is the product of crosslinking of crosslinkable groups located on side chains or as branch end terminal groups, preferably as branch end terminal groups of the first polymer. Non-limiting examples of crosslinkable groups include vinyl groups, acrylate groups, methacrylate groups, glycidyl groups, mercapto groups, or combinations of two or more of these.

[0061] The molecular weight of the first polymer, e.g., its number average molecular weight, can be in the range of 500 to 5,000,000, or 5,000 to 1,000,000, or 20,000 to 500,000. Of course, in the case of crosslinked polymers, it is understood that this molecular weight is calculated before crosslinking.

[0062] The first polymer may be present in the solid electrolyte at a concentration in the solid electrolyte of about 5% to about 80% by weight, about 5% to about 60% by weight, about 5% to about 35% by weight, or about 10% to about 30% by weight, or about 12% to about 25% by weight.

[0063] As described above, the second polymer is different from the first polymer and forms a heterogeneous mixture, i.e., the second polymer is immiscible in the first polymer. The second polymer may consist of a single polymer or a mixture of polymers that form a heterogeneous mixture with the first polymer. The second polymer preferably comprises a substituted polyethylene chain. For example, the polyethylene chain may be substituted with a halogen atom (such as fluorine), an optionally fluorinated alkyl group, an optionally substituted cycloalkyl group, an optionally substituted heterocycloalkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, a polyether group, an optionally fluorinated alkyl ester group, a polyether ester group, or a combination of two or more of these.

[0064] In some cases, the second polymer comprises a copolymer. For example, the copolymer may comprise units substituted with groups selected from halogen atoms (such as fluorine), optionally fluorinated alkyl groups, optionally fluorinated alkyl ester groups, polyether ester groups, or combinations of two or more thereof, and optionally units comprising optionally substituted aryl and / or carboxylic acid groups.

[0065] The second polymer can comprise a random copolymer, a block copolymer, or a combination of random and block copolymers. For example, the block copolymer can comprise at least two blocks comprising different monomers, and at least one of the two blocks comprises a random copolymer sequence.

[0066] Non-limiting examples of monomers that can be used to prepare the second polymer include poly(ethylene glycol) methyl ether (meth)acrylate, (meth)acrylic acid, 1,1-difluorovinyl, tetrafluorovinyl, hexafluoropropene, 2,2,2-trifluoroethyl (meth)acrylate, styrene, divinylbenzene, or a combination of two or more thereof; preferably, the second polymer comprises at least one monomer derived from the polymerization of poly(ethylene glycol) methyl ether (meth)acrylate (PEGMA), 1,1-difluorovinyl, tetrafluorovinyl, hexafluoropropene (HFP), 2,2,2-trifluoroethyl (meth)acrylate, or a combination of two or more thereof, and, optionally, monomers derived from the polymerization of (meth)acrylic acid, styrene, and / or divinylbenzene.

[0067] Examples of the second polymer include, but are not limited to, the following polymers: - poly[styrene- b -poly(poly(ethylene glycol) methyl ether methacrylate- co -methacrylic acid)] (PS- b P(PEGMA- co -MAA); - poly[poly(styrene-co-divinylbenzene)-b-poly(poly(ethylene glycol) methyl ether methacrylate-co-methacrylic acid)] (P(S-co-DVB-bP(PEGMA-co-MAA); - Poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP); - poly[(2,2,2-trifluoroethyl methacrylate)-co-(poly(ethylene glycol) methyl ether methacrylate)] (PTFEMA-co-PEGMA); Or a combination of at least two of these.

[0068] In some examples, the second polymer comprises poly[styrene-b-poly(poly(ethylene glycol) methyl ether methacrylate-co-methacrylic acid)] (PS-bP(PEGMA-co-MAA), poly[poly(styrene-co-divinylbenzene)-b-poly(poly(ethylene glycol) methyl ether methacrylate-co-methacrylic acid)] (P(S-co-DVB)-bP(PEGMA-co-MAA), or a combination of both. For example, the second polymer may comprise poly[poly Poly(styrene-co-divinylbenzene)-b-poly(poly(ethylene glycol) methyl ether methacrylate-co-methacrylic acid)] (P(S-co-DVB)-bP(PEGMA-co-MAA). According to another example, the second polymer comprises poly(vinylidene fluoride)-co-hexafluoropropylene, poly[(2,2,2-trifluoroethyl methacrylate)-co-(poly(ethylene glycol) methyl ether methacrylate)], or a combination of both.

[0069] In some examples, the second polymer is a mixture of at least two of the polymers defined for the second polymer. For example, the mixture of at least two polymers can include poly(vinylidene fluoride)-co-hexafluoropropylene and one of the polymers described above.

[0070] The molecular weight of the second polymer, for example, its number average molecular weight, can be in the range of 5 million to 5 million, or 5,000 to 1,000,000, or 20,000 to 500,000.

[0071] The second polymer, when mixed with the first polymer, is preferably in the form of particles (e.g., microparticles, nanoparticles, picoparticles, or a mixture comprising two or more of these), powders, fibers, rods, vesicles, micelles, etc. The second polymer can also be dissolved in a solvent in which it is miscible.

[0072] The weight concentration of the second polymer (or combination of second polymers) in the solid electrolyte is preferably about 3 wt % to about 40 wt %, about 4 wt % to about 30 wt %, about 4 wt % to about 25 wt %, about 8 wt % to about 20 wt %, or about 10 wt % to about 18 wt % in the solid electrolyte.

[0073] In some examples, the solid electrolyte further comprises a third polymer different from the first polymer and the second polymer, for example, the third polymer can be an optionally substituted, preferably phosphorus-containing polysaccharide (such as cellulose fiber), or a combination thereof.

[0074] According to some embodiments, an ionic organic additive is present in the solid electrolyte composition. For example, the ionic organic additive may be present in the solid electrolyte at a concentration of about 0.5% to about 35% by weight, or about 2% to about 30% by weight, or about 5% to about 20% by weight.

[0075] Ionic organic additives can be in the form of liquid or solid, and can be monofunctional or polyfunctional, preferably bifunctional.Examples of organic additives include the ionic compounds described in patent applications WO2022 / 165598 and WO2023 / 133642.For example, ionic organic additives can be represented by formula I or II: [ka] [In the formula, A - is a delocalized anion, R + -N + (R1R2R3) and -P + (R1R2R3) group, R1, R2, and R3 are independently substituted or unsubstituted linear or branched C 1~12alkyl groups; or R1 and R2 together with the nitrogen or phosphorus atom form a heterocycle having one or more rings and 3 to 12 members, and R3 is as previously defined; or R1, R2, and R3 together with the nitrogen or phosphorus atom form a heteroaromatic or partially unsaturated heterocycle 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. The ionic bifunctional molecule may include:

[0076] An example of a delocalized anion is the hexafluorophosphate ion (PF6 - ), bis(trifluoromethanesulfonyl)imide ion (TFSI - ), bis(fluorosulfonyl)imide ion (FSI - ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide ion (FTFSI - ), 2-trifluoromethyl-4,5-dicyanoimidazol- ate ion (TDI - ), 4,5-dicyano-1,2,3-triazolate ion (DCTA - ), bis(pentafluoroethylsulfonyl)imide ion (BETI - ), difluorophosphate ion (DFP - ), tetrafluoroborate ion (BF4 - ), bis(oxalato)borate ion (BOB - ), nitrate ions (NO3 - ), perchlorate ion (ClO4 - ), hexafluoroarsenate ion (AsF6 - ), trifluoromethanesulfonate ion (CF3SO3 - or - OTf), fluoroalkyl phosphate ion ([PF3(CF2CF3)3] - or FAP -), tetrakis(trifluoroacetoxy)borate ion ([B(OCOCF3)4] - or TFAB - ), bis(1,2-benzenediolato(2-)-O,O')borate ion ([B(C6O2)2] - or BBB - ), difluoro(oxalato)borate ion (BF2(C2O4) - or FOB - ), and the formula BF2O4R x (R x =C 2~4 alkyl), preferably PF6 - , TFSI - , FSI - , FTFSI - , BF4 - , or CF3SO3 - , more preferably TFSI - This includes, but is not limited to:

[0077] According to some examples, R + -N + (R1R2R3) group, where preferably R1, R2, and R3 are defined according to one of the following options: R1, R2, and R3 are independently substituted or unsubstituted linear or branched C 1~12 selected from alkyl groups; R1, R2, and R3 are independently linear or branched C 1~12 alkyl groups, or at least one of R1, R2, or R3 is substituted with a halogen atom, or an alkoxy group, an ether group, an ester group, or a siloxy group; - R1 and R2 together with the nitrogen atom form a heterocycle having one or more rings and 3 to 12 members, R3 is as defined above, preferably R3 is C 1~12 Alkyl, or C 1~4 is alkyl; or R1, R2 and R3 together with the nitrogen atom form a heteroaromatic or partially unsaturated heterocycle having one or more rings and 5 to 12 members.

[0078] According to some embodiments, R + teeth, [ka] wherein R3 is as defined above and R4 is a substituted or unsubstituted linear or branched C 1~12 Alkyl group, C 1~12 Alkenyl group, or C 1~12 Alkynyl groups, preferably C 1~4 R5 is a hydrogen atom or a substituted or unsubstituted linear or branched C 1~12 Alkyl group, C 1~12 Alkenyl group or C 1~12 The heterocycle is an optionally substituted alkynyl group, preferably C 1~4 alkyl group] For example, R3 may be selected from unsubstituted C 1~4 It may be an alkyl group, such as a methyl, ethyl, n-propyl or i-propyl group, or an n-butyl, i-butyl, s-butyl or t-butyl group.

[0079] According to an alternative embodiment, R + -P + (R1R2R3) group, preferably R1, R2, and R3 are independently substituted or unsubstituted linear or branched C 1~12 alkyl groups; or R1, R2, and R3 are independently linear or branched C 1~12 alkyl groups, or at least one of R1, R2, or R3 is substituted with a halogen atom, or an alkoxy group, an ether group, an ester group, or a siloxy group.

[0080] According to one example, the ionic organic additive is of formula I, where the variable n is a number ranging from 2 to 10, or from 3 to 8, or from 4 to 6.

[0081] Non-limiting examples of ionic organic additives include 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, 3,3′-(1,6-hexamethylene)bis(1,2-dimethylimidazolium)bis(trifluoromethanesulfonyl)imide, or a combination of one or more thereof.

[0082] In some examples, the solid electrolyte further includes a plasticizer, such as a non-reactive, relatively high-boiling organic liquid. The plasticizer may be present in the solid electrolyte at a concentration of, for example, about 5% to about 50% by weight, about 10% to about 40% by weight, or about 20% to about 30% by weight. It is understood that the concentration of the plasticizer is adjusted so that the produced electrolyte film remains solid. Examples of plasticizers include, but are not limited to, glycol diethers (such as tetraethylene glycol dimethyl ether (TEGDME), also known as tetraglyme), carbonates (such as propylene carbonate, ethylene carbonate, and fluoroethylene carbonate), lactones (such as γ-butyrolactone), adiponitrile, and ionic liquids, preferably glycol diether liquids (such as TEGDME).

[0083] In some examples, the solid electrolyte further comprises a salt such as an alkali metal salt, preferably a lithium salt, preferably at a concentration of about 5% to about 40% by weight, or about 15% to about 40% by weight, or about 20% to about 35% by weight in the solid electrolyte. Non-limiting examples of salts include those containing an alkali metal (preferably lithium) cation and an anion, such as hexafluorophosphate (PF6 - ), bis(trifluoromethanesulfonyl)imide ion (TFSI - ), bis(fluorosulfonyl)imide ion (FSI - ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide ion ((FSI)(TFSI) - ), 2-trifluoromethyl-4,5-dicyanoimidazol- ate ion (TDI - ), 4,5-dicyano-1,2,3-triazolate ion (DCTA - ), bis(pentafluoroethylsulfonyl)imide ion (BETI - ), difluorophosphate ion (DFP - ), tetrafluoroborate ion (BF4 - ), bis(oxalato)borate ion (BOB - ), nitrate ions (NO3 - ), chloride ions (Cl - ), bromide ion (Br - ), fluoride ion (F - ), perchlorate ion (ClO4 - ), hexafluoroarsenate ion (AsF6 - ), trifluoromethanesulfonate ion (SO3CF3 - )(Tf - ), fluoroalkyl phosphate ion [PF3(CF2CF3)3 - ](FAP - ), tetrakis(trifluoroacetoxy)borate ion [B(OCOCF3)4] - (TFAB - ), bis(1,2-benzenediolato(2-)-O,O')borate ion [B(C6O2)2] - (B.B.B. -), difluoro(oxalato)borate ion (BF2(C2O4) - )(FOB - ), formula BF2O4R x - (In the formula, R x =C 2~4 and an anion selected from the group consisting of anions of (alkyl), and one of the combinations thereof, for example, LiTFSI or LiFSI.

[0084] This document also describes a process for preparing a solid electrolyte membrane as defined herein, for example, the process comprising: a) mixing a first polymer, a second polymer, optionally a plasticizer, optionally an ionic organic additive, optionally a salt, and optionally a solvent to obtain a mixture; b) applying the mixture obtained in (a) onto a substrate to form a coating layer; c) removing the solvent if necessary Includes.

[0085] In some cases, the process further comprises preparing the first polymer and / or the second polymer, preferably preparing the second polymer. Step (a) may comprise a sequential mixing step. For example, if a plasticizer, a salt, and / or an ionic organic additive type additive is included, one or more of these can be mixed with one of the two polymers or their precursors before forming it and before mixing it with the other of the two polymers.

[0086] The solvent, when present, is preferably an inert organic solvent, preferably one that is relatively volatile, for example, an ether (such as tetrahydrofuran), a ketone (such as acetone), or the like.

[0087] Step (b) of the process can be carried out by conventional application techniques including printing such as doctor blade coating, comma coating, inverse comma coating, gravure coating, slot die coating, spray deposition, dipping, drop casting, mold casting, extrusion coating, spin coating, etc. Preferably, step (b) is carried out by a coating method.

[0088] In some examples, at least one of the first polymer and the second polymer contains a crosslinkable group, preferably the first polymer.The method may then include a crosslinking step, for example, by heat treatment, by irradiation (UV, microwave, gamma ray, X-ray, electron beam, etc.), or a combination of these two, optionally in the presence of a crosslinking agent added in step (a).The crosslinking step is carried out after step (b) or, if step (c) is present, after step (c).

[0089] The present technology also relates to an electrochemical cell comprising a solid electrolyte as described herein between a negative electrode and a positive electrode.

[0090] For example, the positive electrode includes a positive electrode material including a positive electrode electrochemically active material, optionally on a current collector. For example, the positive electrode electrochemically active material can be selected from metal phosphates, lithium metal phosphates, metal oxides, and lithium metal oxides. Examples of positive electrode electrochemically active materials include LiM'PO4 (where M' is Fe, Ni, Mn, Co, or a combination of at least two of these), LiVO, VOF, LiVO, LiMnO, Li 1+w M''O 2-a X b (M'' is Mn, Co, Ni, Mg, Al, Zr, W, Ti, Nb, V, Fe, Mo, or a combination thereof (NMC, Li 1+w Mn x Co y Ni z O2, etc.), and X is F, S, or a combination thereof), Li 1+w(NiM''')O2 (M''' is Mn, Co, Mg, Al, W, Fe, Cr, Ti, Zr, Nb, Mo, V, or a combination thereof), elemental sulfur, selenium or iodine, iron(III) fluoride, copper(II) fluoride, lithium iodide, carbon-based active materials, organic cathode active materials, or a combination of two or more of these, if compatible with each other.

[0091] The positive electrode electrochemically active material can be in the form of optionally coated particles (eg, of polymer, ceramic, carbon, or a combination of two or more of these).

[0092] The positive electrode material may further comprise a binder, an electronically conductive material, a salt, an ionic organic additive, inorganic particles, or a combination of two or more of these.

[0093] The negative electrode also includes a negative electrode material, including a negative electrode electrochemically active material, optionally on a current collector.

[0094] In some examples, the negative electrode electrochemically active material film is a metal film comprising an alkali metal or alkaline earth metal, or an alloy containing an alkali metal or alkaline earth metal. For example, the metal film is selected from a lithium film, a lithium alloy film, a sodium film, a sodium alloy film, a magnesium film, or a magnesium alloy film, preferably a lithium film or a sodium film, or an alloy containing one of these two, preferably a lithium film or a lithium alloy film. The lithium alloy preferably comprises at least 50 wt%, or at least 75 wt%, or at least 90 wt%, or at least 95 wt%, or at least 99 wt% lithium.

[0095] When the metal film is a lithium alloy, it may contain, in addition to lithium, an element selected from alkali metals other than lithium (such as Na, K, Rb, and Cs), alkaline earth metals (such as Mg, Ca, Sr, and Ba), rare earth metals (such as Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), zirconium, copper, silver, bismuth, cobalt, manganese, zinc, aluminum, silicon, tin, antimony, cadmium, mercury, lead, molybdenum, iron, boron, indium, thallium, nickel, and germanium (e.g., Zr, Cu, Ag, Bi, Co, Zn, Al, Si, Sn, Sb, Cd, Hg, Pb, Mn, B, In, Tl, Ni, or Ge).

[0096] Alternatively, the negative electrode electrochemically active material may be an intermetallic compound (e.g., SnSb, TiSnSb, CuSb, AlSb, FeSb, FeSn, and CoSn), a metal oxide, a metal nitride, a metal phosphide, a metal phosphate (e.g., LiTi(PO)), 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), a silicon-carbon composite (Si-C), a silicon oxide (SiO x ), silicon oxide-carbon composite (SiO x -C), tin (Sn), tin-carbon composite (Sn-C), tin oxide (SnO x ), tin oxide-carbon composite (SnO x -C), and combinations thereof, where compatible. For example, the metal oxide may be of the formula M"" b O cCompounds of M'''' where M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof, and b and c are numbers such that the c:b ratio is in the range of 2 to 3 (e.g., MoO3, MoO2, MoS2, V2O5, and TiNb2O7), spinel oxides (e.g., NiCo2O4, ZnCo2O4, MnCo2O4, CuCo2O4, and CoFe2O4), and LiM''''O where M'''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof (e.g., lithium titanate (Li4Ti5O 12 ) or lithium and molybdenum oxide (Li2Mo4O 13 etc.)

[0097] The negative electrode electrochemically active material can be in the form of optionally coated particles (eg, of polymer, ceramic, carbon, or a combination of two or more of these).

[0098] The negative electrode material may also include a binder, an electronically conductive material, a salt, an ionic organic additive, inorganic particles, or a combination of two or more of these.

[0099] When present in the negative electrode and / or positive electrode, the binder may comprise a polymer as defined for the first polymer and the second polymer. The binder polymer may comprise ion-solvating units, particularly lithium ions. Examples of solvating polymers include linear or branched polyether polymers (e.g., PEO, PPO, or EO / PO copolymers), poly(dimethylsiloxane), poly(alkylene carbonate), poly(alkylene sulfone), poly(alkylene sulfamide), polyurethane, poly(vinyl alcohol), polyacrylonitrile, polymethyl methacrylate, and copolymers thereof, optionally containing crosslinked units derived from crosslinkable functional groups (such as acrylate, methacrylate, vinyl, glycidyl, or mercapto functional groups).

[0100] The binder, if present, may also be a rubber-type electrode binder such as SBR (styrene butadiene rubber), NBR (acrylonitrile butadiene rubber), HNBR (hydrogenated NBR), CHR (epichlorohydrin rubber), and ACM (acrylate rubber), or a fluoropolymer-type binder such as PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), and combinations thereof. Some binders, such as rubber-type binders, may also include additives such as CMC (carboxymethyl cellulose).

[0101] Examples of electronically conductive materials that can be included in the electrode material include carbon black (e.g., Ketjen™, Denka™, Shawinigan carbon, acetylene black, etc.), graphite, graphene, carbon nanotubes, carbon fibers (including carbon nanofibers, vapor-grown carbon fibers (VGCF), etc.), non-powdered carbon obtained by carbonization of organic precursors (e.g., as a coating on particles), or a combination of two or more of these.

[0102] This document also relates to a battery or electrochemical accumulator comprising at least one electrochemical cell as defined herein. For example, the battery can be selected from 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. Preferably, the battery is a lithium battery or a lithium ion battery.

[0103] The batteries and electrochemical accumulators described herein are intended for use in portable devices such as, for example, mobile phones, cameras, tablets, or laptops, electric or hybrid vehicles, or renewable energy storage. [Example]

[0104] The following examples are for illustrative purposes and should not be construed as further limiting the scope of the invention as contemplated. These examples are better understood by reference to the accompanying figures.

[0105] Unless otherwise indicated, all numbers expressing amounts of ingredients, reaction conditions, concentrations, properties, stability, and the like used in the application and claims should be understood to be modified in all instances by the term "about." At the very least, each numerical parameter should be construed in light of the number of reported significant digits and by applying conventional rounding techniques. Accordingly, unless otherwise indicated, the numerical parameters set forth in this application and the appended claims are approximations that may vary depending upon the properties sought to be achieved. Notwithstanding that the numerical ranges and parameters setting forth the general scope of the embodiments are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently contains some errors resulting from variations in experiments, testing measurements, statistical analyses, and the like.

[0106] Example 1 Preparation of electrolyte films In the following examples, Polymer 1 is a polyether-type, four-arm star-shaped multi-arm polymer containing crosslinkable units at the ends of the arms as described in U.S. Patent No. 7,897,674. The compositions of Films 1-10 are shown in Table 1. [Table 1]

[0107] a) Film 1 (reference) 2 g of lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), 8 g of polymer 1, and 0.08 g of Irgacure™ were mixed in a flask at room temperature. Once a homogeneous solution was obtained, the solution was coated onto a thin stainless steel plate. After 3 minutes of UV irradiation under nitrogen, a film of solid polymer electrolyte 1 was thus obtained.

[0108] b) Film 2 According to the procedure described in Xuewei Zhang et al., Chemistry - A European Journal, 2014, 20 (47), 15505-15517, a M of approximately 950 g / mol was obtained. n Poly[styrene-b-poly(poly(ethylene glycol methyl ether methacrylate)-co-methacrylic acid)] nanoparticles (PS-NPs) were prepared using PEGMA with

[0109] Then, 4.05 g of these PS-NP nanoparticles, 6 g of additive, 9.6 g of TEGDME, and 3 g of THF were mixed in a flask at room temperature. After 2 hours, 6.75 g of polymer 1 was added. The mixture was stirred with a magnetic bar for 1 hour. Then, 7.2 g of LiTFSI was added. After 4 hours of stirring, 0.15 g of Irgacure™ was added. The solution was coated onto a polypropylene film. The solvent was evaporated at 20°C. After 5 minutes of UV irradiation under nitrogen, a film of solid polymer electrolyte 2 was thus obtained.

[0110] c) Film 3 The macromolecular chain transfer agent, poly(ethylene glycol methyl ether methacrylate)- co -methacrylic acid) trithiocarbonate (macro-CTA), was prepared as described in reference Xuewei Zhang et al. (see (b) for references).

[0111] Next, 0.36 g of macro-CTA, 1.92 g of LiTFSI, and 2.56 g of TEGDME were mixed in a flask at 60°C. After 2 hours, the solution was cooled, and 0.72 g of styrene, 0.018 g of divinylbenzene (approximately a 4:1 para:meta mixture), and 0.0013 g of AIBN were added. The solution was deoxygenated at 0°C for 30 minutes and then heated to 80°C with stirring for 4 hours to obtain PS-NP-2 nanoparticles. After cooling, 2 g of THF and 1.6 g of additives were added. Once a homogeneous emulsion was obtained, 1.8 g of polymer 1 and 0.15 g of Irgacure™ were added. After stirring for 1 hour, the solution was coated onto a polypropylene film, and the solvent was evaporated at 20°C. After 5 minutes of UV irradiation under nitrogen, a solid polymer electrolyte film 3 was thus obtained.

[0112] Figure 1 shows a transmission electron microscope (TEM) image of PS-NP-2 nanoparticles before the addition of other components of the solid electrolyte.

[0113] d) Film 4 Film 4 was prepared according to the preparation protocol for Film 3 described in (c), with the proportions of each component being as shown in Table 1 above.

[0114] e) Film 5 Molecular weight (M) of approximately 400,000 g / mol w PVDF-HFP (1.08 g) having the formula (I) was dissolved in 7 g of acetone at 50° C. in a flask. After cooling, 0.8 g of an additive was added, and the solution was stirred at 50° C. for 4 hours. Then, 2.96 g of LiTFSI and 2.32 g of TEGDME were added. The solution was stirred at room temperature for 2 hours. 1.8 g of polymer 1 and 0.02 g of Irgacure™ were added. After stirring for 1 hour, the solution was coated onto a polypropylene film. The solvent was evaporated at 20° C. After 5 minutes of UV irradiation under nitrogen, a solid polymer electrolyte film 5 was thus obtained.

[0115] f) Film 6 Film 6 was prepared according to the preparation protocol for Film 5 described in (e), with the proportions of each component being as shown in Table 1 above.

[0116] g) Film 7 The synthesis of PS-NP-2 was carried out as previously described for film 3, using the same amounts. After the synthesis was completed, a solution of PVDF-HFP (0.4 g) in acetone (6 g) and 0.8 g of additive were added. The mixture was stirred at 60 °C for 4 hours. Then, 1.4 g of polymer 1 and 0.02 g of Irgacure™ were added at room temperature. After stirring for 1 hour, the solution was coated onto a polypropylene film, and the solvent was evaporated at 20 °C. After 5 minutes of UV irradiation under nitrogen, solid polymer electrolyte film 7 was thus obtained.

[0117] h) Film 8 Film 8 was prepared according to the preparation protocol for Film 5 described in (e). The phosphorus-containing cellulose fibers (CNF) were added before the addition of Polymer 1. The proportions of each component are as shown in Table 1 above.

[0118] i) Film 9 Film 9 was prepared according to the preparation protocol for Film 5 described in (e). The phosphorus-containing cellulose fibers (CNF) were added before the addition of Polymer 1. The proportions of each component are as shown in Table 1 above.

[0119] j) Film 10 2.96 g of LiTFSI and 2.32 g of TEGDME were mixed thoroughly in a flask at 80° C. for 24 hours. 0.6 g of 2,2,2-trifluoroethyl methacrylate, 0.1 g of poly(ethylene glycol) methacrylate (M n500 g / mol) and 0.002 g of AIBN were added at room temperature. After 30 minutes of deoxygenation, the solution was heated to 80°C for 1 hour with stirring. Then, a solution of PVDF-HFP (0.38 g) in acetone (3 g) and 0.8 g of additive were added at room temperature. The solution was stirred at 60°C for 4 hours. 1.8 g of Polymer 1 and 0.02 g of Irgacure™ were added at room temperature. After 1 hour of stirring, the solution was coated onto a polypropylene film and the solvent was evaporated at 20°C. After 5 minutes of UV irradiation under nitrogen, a solid polymer electrolyte film was thus obtained.

[0120] Example 2 Physicochemical properties a) Differential scanning calorimetry The thermal behavior of the PVDF-HFP film, the PVDF-HFP / ionic additive mixture film (weight ratio: 1.725 / 1, identical to that of Film 6), and Film 6 were investigated using a TA® DSC2500 instrument under nitrogen at a heating and cooling rate of 10 °C / min from -50 °C to 200 °C. Air was used as the analytical standard. The instrument was calibrated with indium prior to analysis. The results are shown in Figure 2.

[0121] The PVDF-HFP / ionic additive mixture exhibited a lower crystallinity ratio compared to that of PVDF-HFP alone, indicating interactions between the PVDF-HFP chains and the additive molecules. In contrast, the crystallinity ratio of Film 6 was higher than that of PVDF-HFP alone. This phenomenon could be explained by the reorganization of the PVDF-HFP chains in the presence of LiTFSI salt. Electrochemical results indicated that this chain reorganization facilitated battery cycling.

[0122] b) Young's modulus of the membrane For the membrane prepared in Example 1(f) containing Film 6, the Young's modulus was evaluated at 20°C in an Instron® 5944 instrument. The film size for measurement is 50 mm x 13 mm x 0.045 mm (length x width x thickness). The speed is 100 mm / min. Figure 3 shows a graph of the Young's modulus of the Film 6 membrane. The Young's modulus of this membrane is 1.5 MPa.

[0123] c) Diffusion coefficient The ionic diffusion coefficients of different elements in the films prepared in Example 1 (4 and 5) are 1 H, 7 Li, and 19 The NMR experiments were performed using a Diff50™ probe and a 1000 Hz pulsed field gradient solid-state NMR spectroscopy of F nuclei. 7 Li- 19 F and 1 H- 19 It was performed on a 500 MHz NMR spectrometer equipped with a F double-resonance RF insert.

[0124] Measurements were performed at temperatures between 5°C and 70°C. Gradient pulse durations ranged from 1.0 to 2.0 ms, and diffusion times ranged from 40 to 100 ms depending on the nucleus. Gradient strengths were varied from 100 G / cm to 2500 G / cm in 16 steps.

[0125] Diffusion measurements were accompanied by T2-related experiments using CPMG pulse sequences with echo delays of 0.06–0.6 ms. Up to 64 echoes were collected per experiment. The results are shown in Table 2. [Table 2]

[0126] Transference number “t” + is calculated based on the assumption that the salt dissociates completely without the formation of ionic aggregates.

[0127] Example 3 Electrochemical properties a) Cell assembly (symmetrical battery) For ionic conductivity measurements, symmetric coin cells of stainless steel / electrolyte / stainless steel type were assembled. A polymer electrolyte membrane disk was cut to a diameter of 16 mm and sandwiched between two electrodes. The configuration of each cell is as follows (electrodes = stainless steel): - Cell 1: electrode / Example 1 (Film 1) / electrode; - Cell 2: electrode / Example 1 (film 3) / electrode; Cell 3: electrode / Example 1 (Film 5) / electrode; and - Cell 4: electrode / Example 1 (film 8) / electrode.

[0128] b) Ionic conductivity Electrochemical impedance spectroscopy was performed using a Bio-logic® VMP-300 system at an amplitude of 100 mV and a frequency range of 1 MHz to 200 mHz. The results are shown in Table 3 below. Figure 4 also shows the ionic conductivities of cells 1-4.

[0129] c) Complete Battery Assembly The cathode was prepared using a SiO 2 solution containing approximately 8 mg / cm 2 as described in International Patent Application WO 2023 / 133640. 2 The lithium nickel manganese cobalt oxide (LiNi 0,8 Mn 0,1 Co 0,1 The electrolyte film was bonded onto the cathode at 75 psi air pressure and 50°C for 5 minutes. A lithium metal foil with a thickness of approximately 50 μm was then bonded onto the electrolyte film as the anode. Then, a 3.88 cm 2 A coin cell was assembled and its performance was evaluated.

[0130] Complete cells using the solid electrolytes (films 2-10) described in Example 1 were assembled and their performance evaluated. The composition of each cell is shown below (NMC811 = previous NMC811 cathode, Li = 40-50 μm thick lithium metal anode): - Battery 1: NMC811 / Example 1 (Film 2) / Li - Battery 2: NMC811 / Example 1 (Film 3) / Li - Battery 3: NMC811 / Example 1 (Film 4) / Li - Battery 4: NMC811 / Example 1 (Film 5) / Li - Battery 5: NMC811 / Example 1 (Film 6) / Li - Battery 6: NMC811 / Example 1 (Film 7) / Li - Battery 7: NMC811 / Example 1 (Film 8) / Li - Battery 8: NMC811 / Example 1 (Film 9) / Li - Battery 9: NMC811 / Example 1 (film 10) / Li

[0131] A reference battery is also prepared in the same manner as Film 1 presented in Example 1.

[0132] d) Full battery performance Performance evaluation was performed in a Bio-Logic® BCS-810 system at 45°C, with voltages of 2.75 to 4.2 V and currents of C / 6 to 1 C and C / 3 to 1 C (1 C = 1.2 mA / cm). 2 The battery capacity was approximately 4.4mAh (1.2mAh / cm 2 ) Figure 5 shows the capacity of batteries containing films 2-10 (batteries 1-9) as a function of the number of cycles. Table 3 also shows the number of cycles reached before reaching a 20% capacity loss. [Table 3]

[0133] The reference battery failed cycling at C / 6 to 1C, which is believed to be due to poor adhesion between the electrolyte film and metallic lithium.

[0134] Various modifications could be made to any of the above embodiments without departing from the scope of the invention as contemplated. Any references, patents, or scientific literature documents referred to in this application are incorporated herein by reference in their entirety for all purposes.

Claims

1. 1. A solid electrolyte comprising a first polymer, a second polymer, optionally a plasticizer, and optionally an ionic organic additive, wherein the first polymer is a branched polyether having at least three branches, and the first polymer and second polymer are different and form a heterogeneous mixture.

2. 10. The solid electrolyte of claim 1, wherein the first polymer is a branched polyether having at least four branches in a star configuration.

3. 3. The solid electrolyte of claim 1, wherein the branches of the first polymer comprise polymer chains of alkylene oxide units.

4. 4. The solid electrolyte of claim 3, wherein the alkylene oxide units comprise ethylene oxide units, propylene oxide units, or a combination of ethylene oxide and propylene oxide units.

5. 5. The solid electrolyte according to claim 1, wherein the first polymer is crosslinkable and comprises crosslinkable groups, for example located on side chains or as terminal groups at the ends of branches, preferably as terminal groups at the ends of branches.

6. 5. A solid electrolyte according to claim 1, wherein the first polymer is further crosslinked, the polymer being the product of crosslinking of crosslinkable groups, for example located on side chains or as terminal groups at the ends of branches, preferably as terminal groups at the ends of branches of the first polymer.

7. 7. The solid electrolyte according to claim 5, wherein the crosslinkable groups are selected from vinyl groups, acrylate groups, methacrylate groups, glycidyl groups, and mercapto groups, and combinations of at least two of these.

8. 8. The solid electrolyte of claim 1, wherein the first polymer has a number average molecular weight of 5 million to 5 million, or 5,000 to 1,000,000, or 20,000 to 500,000.

9. 9. The solid electrolyte of claim 1, wherein the first polymer is present in the solid electrolyte at a concentration of about 5 wt % to about 80 wt %, about 5 wt % to about 60 wt %, about 5 wt % to about 35 wt %, or about 10 wt % to about 30 wt %, or about 12 wt % to about 25 wt %.

10. 10. The solid electrolyte of claim 1, wherein the second polymer comprises substituted polyethylene chains.

11. 11. The solid electrolyte of claim 1, wherein the second polymer comprises groups selected from fluorine, optionally fluorinated alkyl groups, optionally substituted cycloalkyl groups, optionally substituted heterocycloalkyl groups, optionally substituted aryl groups, optionally substituted heteroaryl groups, polyether groups, optionally fluorinated alkyl ester groups, polyether ester groups, or combinations of two or more of these.

12. 12. The solid electrolyte of claim 1, wherein the second polymer comprises a copolymer.

13. 13. The solid electrolyte of claim 12, wherein the second polymer comprises a copolymer, the copolymer comprising units comprising groups selected from fluorine, optionally fluorinated alkyl groups, optionally fluorinated alkyl ester groups, polyether ester groups, or combinations of two or more thereof, and optionally units comprising optionally substituted aryl and / or carboxylic acid groups.

14. 14. The solid electrolyte of claim 12 or 13, wherein the second polymer comprises a random copolymer or a block copolymer, or a combination of a random copolymer and a block copolymer.

15. 15. The solid electrolyte of claim 14, wherein the second polymer comprises a block copolymer comprising at least two blocks of different monomers, at least one of the two blocks comprising a random copolymer sequence.

16. 16. The solid electrolyte of any one of claims 1 to 15, wherein the second polymer comprises at least one monomer derived from the polymerization of poly(ethylene glycol) methyl ether (meth)acrylate, (meth)acrylic acid, 1,1-difluorovinyl, tetrafluorovinyl, hexafluoropropene, 2,2,2-trifluoroethyl (meth)acrylate, styrene, divinylbenzene, or a combination of two or more thereof; preferably, the second polymer comprises at least one monomer derived from the polymerization of poly(ethylene glycol) methyl ether (meth)acrylate (PEGMA), 1,1-difluorovinyl (PVDF), tetrafluorovinyl (PTFE), hexafluoropropene (HFP), 2,2,2-trifluoroethyl (meth)acrylate, or a combination of two or more thereof, and optionally monomers derived from the polymerization of (meth)acrylic acid, styrene, and / or divinylbenzene.

17. the second polymer is - poly[styrene-b-poly(poly(ethylene glycol) methyl ether methacrylate-co-methacrylic acid)] (PS-b-P(PEGMA-co-MAA); - poly[poly(styrene-co-divinylbenzene)-b-poly(poly(ethylene glycol) methyl ether methacrylate-co-methacrylic acid)] (P(S-co-DVB)-b-P(PEGMA-co-MAA); poly(vinylidene fluoride)-co-hexafluoropropylene; and - poly[(2,2,2-trifluoroethyl methacrylate)-co-(poly(ethylene glycol) methyl ether methacrylate))]; or a combination of at least two of these 17. The solid electrolyte of claim 16, comprising a polymer selected from:

18. 18. The solid electrolyte of claim 17, wherein the second polymer comprises poly[styrene-b-poly(poly(ethylene glycol) methyl ether methacrylate-co-methacrylic acid)] (PS-b-P(PEGMA-co-MAA), poly[poly(styrene-co-divinylbenzene)-b-poly(poly(ethylene glycol) methyl ether methacrylate-co-methacrylic acid)] (P(S-co-DVB)-b-P(PEGMA-co-MAA), or a combination of the two.

19. 18. The solid electrolyte of claim 17, wherein the second polymer comprises poly(vinylidene fluoride)-co-hexafluoropropylene, poly[(2,2,2-trifluoroethyl methacrylate)-co-(poly(ethylene glycol) methyl ether methacrylate)], or a combination thereof.

20. 20. A solid electrolyte according to any one of claims 1 to 19, wherein the second polymer is a mixture of at least two polymers as previously defined.

21. 21. The solid electrolyte of claim 20, wherein said mixture of at least two polymers comprises at least poly(vinylidene fluoride)-co-hexafluoropropylene.

22. 22. The solid electrolyte of any one of claims 1 to 21, wherein the second polymer has a number average molecular weight of 5 million to 5 million, or 5,000 to 1,000,000, or 20,000 to 500,000.

23. 23. The solid electrolyte of claim 1, wherein the second polymer is in the form of particles (e.g., microparticles, nanoparticles, picoparticles, or a mixture comprising two or more of these), such as a powder, fibers, rods, vesicles, micelles, or the like.

24. 24. The solid electrolyte of any one of claims 1 to 23, wherein the second polymer is present in the solid electrolyte at a concentration of about 3 wt % to about 40 wt %, about 4 wt % to about 30 wt %, 4 wt % to about 25 wt %, or about 8 wt % to about 20 wt %, or about 10 wt % to about 18 wt %.

25. 25. The solid electrolyte of claim 1, further comprising a third polymer different from the first polymer and the second polymer.

26. 26. The solid electrolyte of claim 25, wherein the third polymer is an optionally substituted, preferably phosphorus-containing, polysaccharide (such as cellulose fiber), or a combination thereof.

27. 27. The solid electrolyte of any one of claims 1 to 26, wherein the ionic organic additive is present in the solid electrolyte at a concentration of preferably from about 0.5 wt % to about 35 wt %, or from about 2 wt % to about 30 wt %, or from about 5 wt % to about 20 wt %.

28. The ionic organic additive is represented by Formula I or II: 【Transformation 5】 is a bifunctional ionic molecule of the formula: A － is a delocalized anion, R ＋ is -N ＋ (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 atom or the phosphorus atom, form a heterocycle 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 atom or phosphorus atom form a heteroaromatic or partially unsaturated heterocycle 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; 28. The solid electrolyte of claim 27.

29. The delocalized anion is a hexafluorophosphate ion (PF ６ － ), bis(trifluoromethanesulfonyl)imide ion (TFSI － ), bis(fluorosulfonyl)imide ion (FSI － ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide ion (FTFSI － ), 2-trifluoromethyl-4,5-dicyanoimidazol- ate ion (TDI － ), 4,5-dicyano-1,2,3-triazolate ion (DCTA － ), bis(pentafluoroethylsulfonyl)imide ion (BETI － ), difluorophosphate ion (DFP － ), tetrafluoroborate ion (BF ４ － ), bis(oxalato)borate ion (BOB － ), nitrate ions (NO ３ － ), perchlorate ion (ClO ４ － ), hexafluoroarsenate ion (AsF ６ － ), trifluoromethanesulfonate ion (CF ３ SO ３ － or － OTf), fluoroalkyl phosphate ion ([PF ３ (CF ２ CF ３ ) ３ ] － or FAP － ), tetrakis(trifluoroacetoxy)borate ion ([B(OCOCF ３ ) ４ ] － or TFAB － ), bis(1,2-benzenediolato(2-)-O,O')borate ion ([B(C ６ O ２ ) ２ ] － or BBB － ), difluoro(oxalato)borate ion (BF ２ (C ２ O ４ ) － or FOB － ), and formula BF ２ O ４ R ｘ (R ｘ =C ２～４ 29. The solid electrolyte of claim 28, wherein the anion is selected from the group consisting of:

30. The delocalized anion is a hexafluorophosphate ion (PF ６ － ), bis(trifluoromethanesulfonyl)imide ion (TFSI － ), bis(fluorosulfonyl)imide ion (FSI － ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide ion (FTFSI － ), tetrafluoroborate ion (BF ４ － ), and trifluoromethanesulfonate ion (CF ３ SO ３ － or － 30. The solid electrolyte of claim 29, wherein the solid electrolyte is selected from the group consisting of SiO2, ...

31. The delocalized anion is a bis(trifluoromethanesulfonyl)imide ion (TFSI － 31. The solid electrolyte of claim 30, wherein

32. R ＋ But, -N ＋ (R １ R ２ R ３ 32. The solid electrolyte according to claim 28, wherein the aryl group is a aryl group.

33. R １ , R ２ , and R ３ are independently substituted or unsubstituted linear or branched C １～１２ 33. The solid electrolyte of claim 32, wherein the alkyl group is selected from the group consisting of alkyl groups.

34. R １ , R ２ , and R ３ are independently linear or branched C １～１２ alkyl groups, or R １ , R ２ , or R ３ 33. The solid electrolyte of claim 32, wherein at least one of is substituted with a halogen atom, or an alkoxy group, an ether group, an ester group, or a siloxy group.

35. R １ and R ２ together with the nitrogen atom form a heterocycle having one or more rings and 3 to 12 members, R ３ is as defined in claim 25, preferably R ３ But C １～１２ Alkyl, or C １～４ 33. The solid electrolyte of claim 32, wherein the alkyl is alkyl.

36. R １ , R ２ , and R ３ The solid electrolyte of claim 32, wherein, together with the nitrogen atom, forms a heteroaromatic or partially unsaturated heterocycle having one or more rings and 5 to 12 members.

37. R ＋ but, 【Transformation 6】 where R ３ is as defined in claim 25, and R ４ is a substituted or unsubstituted linear or branched C １～１２ Alkyl group, C １～１２ alkenyl group, or C １～１２ is an alkynyl group, and R ５ represents a hydrogen atom or a substituted or unsubstituted linear or branched C １～１２ Alkyl group, C １～１２ Alkenyl group, or C １～１２ an alkynyl group, wherein the heterocycle is optionally substituted; 33. The solid electrolyte of claim 32.

38. R ４ But C １～４ 38. The solid electrolyte of claim 37, wherein the alkyl group is an alkyl group.

39. R ５ But C １～４ 39. The solid electrolyte according to claim 37 or 38, wherein the alkyl group is an alkyl group.

40. R ３ is unsubstituted C １～４ 40. The solid electrolyte of any one of claims 37 to 39, wherein the alkyl group is an alkyl group.

41. R ３ is selected from a methyl group, an ethyl group, an n-propyl group, or an i-propyl group, and an n-butyl group, an i-butyl group, an s-butyl group, or a t-butyl group.

42. R ＋ But, -P ＋ (R １ R ２ R ３ 32. The solid electrolyte according to claim 28, wherein the aryl group is a aryl group.

43. R １ , R ２ , and R ３ are independently substituted or unsubstituted linear or branched C １～１２ 43. The solid electrolyte of claim 42, wherein the alkyl group is selected from the group consisting of alkyl groups.

44. R １ , R ２ , and R ３ are independently linear or branched C １～１２ alkyl groups, or R １ , R ２ , or R ３ 43. The solid electrolyte of claim 42, wherein at least one of is substituted with a halogen atom, or an alkoxy group, an ether group, an ester group, or a siloxy group.

45. 45. The solid electrolyte of any one of claims 28 to 44, wherein n is a number in the range of 2 to 10, or 3 to 8, or 4 to 6.

46. 29. The solid electrolyte of claim 28, wherein the ionic bifunctional molecule is 1,1'-(1,6-hexamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide.

47. 29. The solid electrolyte of claim 28, wherein the ionic bifunctional molecule is 1,1'-(1,12-dodecamethylene)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide.

48. 29. The solid electrolyte of claim 28, wherein the ionic bifunctional molecule is 1,1'-(2,2'-(ethylenedioxy)diethane)bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide.

49. 29. The solid electrolyte of claim 28, wherein the ionic bifunctional molecule is 1,1'-(thiolbis(1,2-ethane))bis(1-methylpyrrolidinium)bis(trifluoromethanesulfonyl)imide.

50. 29. The solid electrolyte of claim 28, wherein the ionic bifunctional molecule is 3,3'-(1,6-hexamethylene)bis(1,2-dimethylimidazolium)bis(trifluoromethanesulfonyl)imide.

51. 51. The solid electrolyte of any one of claims 1 to 50, wherein the plasticizer is present in the solid electrolyte at a concentration of preferably from about 5 wt % to about 50 wt %, or from about 10 wt % to about 40 wt %, or from about 20 wt % to about 30 wt %.

52. 52. The solid electrolyte of claim 51 , wherein the plasticizer is selected from the following types of liquids: glycol diethers (such as tetraethylene glycol dimethyl ether (TEGDME)), carbonate esters, ionic liquids, etc., preferably glycol diether type liquids (such as TEGDME).

53. 53. The solid electrolyte of any one of claims 1 to 52, further comprising an alkali metal salt, preferably a lithium salt, in the solid electrolyte, preferably at a concentration of from about 5 wt% to about 40 wt%, or from about 15 wt% to about 40 wt%, or from about 20 wt% to about 35 wt%.

54. The salt is a mixture of an alkali metal (preferably Li) cation and a hexafluorophosphate ion (PF ６ － ), bis(trifluoromethanesulfonyl)imide ion (TFSI － ), bis(fluorosulfonyl)imide ion (FSI － ), (fluorosulfonyl)(trifluoromethanesulfonyl)imide ion ((FSI)(TFSI) － ), 2-trifluoromethyl-4,5-dicyanoimidazol- ate ion (TDI － ), 4,5-dicyano-1,2,3-triazolate ion (DCTA － ), bis(pentafluoroethylsulfonyl)imide ion (BETI － ), difluorophosphate ion (DFP － ), tetrafluoroborate ion (BF ４ － ), bis(oxalato)borate ion (BOB － ), nitrate ions (NO ３ － ), chloride ions (Cl － ), bromide ion (Br － ), fluoride ion (F － ), perchlorate ion (ClO ４ － ), hexafluoroarsenate ion (AsF ６ － ), trifluoromethanesulfonate ion (SO ３ CF ３ － ) (Tf － ), fluoroalkyl phosphate ion [PF ３ (CF ２ CF ３ ) ３ － ](FAP － ), tetrakis(trifluoroacetoxy)borate ion [B(OCOCF ３ ) ４ ] － (TFAB － ), bis(1,2-benzenediolato(2-)-O,O')borate ion [B(C ６ O ２ ) ２ ] － (BBB － ), difluoro(oxalato)borate ion (BF ２ (C ２ O ４ ) － ) (FOB － ), formula BF ２ O ４ R ｘ － (In the formula, R ｘ =C ２～４ 54. The solid electrolyte of claim 53, comprising an anion selected from the group consisting of anions of: LiTFSI, LiFSI, ...

55. 55. An electrochemical cell comprising a negative electrode, a positive electrode, and an electrolyte, wherein the electrolyte is as defined in any one of claims 1 to 54.

56. 56. The electrochemical cell of claim 55, wherein the positive electrode comprises a positive electrode material comprising a positive electrode electrochemically active material.

57. 57. The electrochemical cell of claim 56, wherein the positive electrode material is on a current collector.

58. 58. The electrochemical cell of claim 56 or 57, wherein the positive electrode electrochemically active material is selected from metal phosphates, lithiated metal phosphates, metal oxides, and lithiated metal oxides.

59. The positive electrode electrochemically active material is LiM'PO ４ (M' is Fe, Ni, Mn, Co, or a combination of at least two of them), LiV ３ O ８ , V ２ O ５ F, LiV ２ O ５ , LiMn ２ O ４ , Li １＋ｗ M''O ２－ａ X ｂ (M″ is Mn, Co, Ni, Mg, Al, Zr, W, Ti, Nb, V, Fe, Mo, or a combination thereof (NMC, Li １＋ｗ Mn ｘ Co ｙ Ni ｚ O ２ and X is F, S, or a combination thereof), Li １＋ｗ (NiM''')O ２ 58. The electrochemical cell of claim 56 or 57, wherein M''' is Mn, Co, Mg, Al, W, Fe, Cr, Ti, Zr, Nb, Mo, V, or a combination thereof, elemental sulfur, selenium or iodine, iron (III) fluoride, copper (II) fluoride, lithium iodide, a carbon-based active material such as graphite, an organic cathode active material, or a combination of two or more of these when compatible with each other.

60. 60. The electrochemical cell of any one of claims 56 to 59, wherein the positive electrode material further comprises an electronically conductive material, a binder, a salt, an ionic organic additive, and / or inorganic particles.

61. 61. The electrochemical cell of any one of claims 55 to 60, wherein the negative electrode comprises a negative electrode material comprising a negative electrode electrochemically active material.

62. 62. The electrochemical cell of claim 61 , wherein the negative electrode material is on a current collector.

63. 63. The electrochemical cell of claim 61 or 62, wherein the negative electrode electrochemically active material comprises a metal film comprising an alkali metal or alkaline earth metal, or an alloy including an alkali metal or alkaline earth metal.

64. 64. The electrochemical cell of claim 63, wherein the alkali metal is selected from lithium and sodium, or an alloy containing lithium or sodium, preferably lithium, or an alloy containing lithium.

65. 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 63. The electrochemical cell of claim 61 or 62, comprising:

66. The metal oxide is represented by the formula M'''' ｂ O ｃ where M"" is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof, and b and c are numbers such that the c:b ratio is in the range of 2 to 3. ３ , MoO ２ , MoS ２ , V ２ O ５ , and TiNb ２ O ７ ), spinel oxides (e.g., NiCo ２ O ４ , ZnCo ２ O ４ , MnCo ２ O ４ , CuCo ２ O ４ , and CoFe ２ O ４ ), and LiM'''O, where M''''' is Ti, Mo, Mn, Ni, Co, Cu, V, Fe, Zn, Nb, or a combination thereof (e.g., lithium titanate (Li ４ Ti ５ O １２ ) or lithium and molybdenum oxide (Li ２ Mo ４ O １３ 66. The electrochemical cell of claim 65, wherein the electrochemical cell is selected from the group consisting of:

67. 67. The electrochemical cell of claim 65 or 66, wherein the negative electrode material further comprises an electronically conductive material, a binder, a salt, an ionic organic additive, and / or inorganic particles.

68. 68. A battery comprising at least one electrochemical cell according to any one of claims 55 to 67.

69. 69. The battery of claim 68, wherein 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.

70. 70. The battery of claim 69, wherein the battery is a lithium battery.

71. 70. The battery of claim 69, wherein the battery is a lithium ion battery.

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