Dicationic ionic liquid electrolytes with high ionic conductivity

Abstract

Described herein is a non-flammable dicationic ionic liquid electrolyte and its synthesis. The electrolyte has a viscosity of 0.01 S cm -1 The use of the non-flammable dicationic ionic liquid electrolyte in various energy storage devices, such as lithium ion batteries, rechargeable batteries, fuel cells, supercapacitors, or solar cells, is also described.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 63 / 311,630, filed February 18, 2022, U.S. Provisional Patent Application No. 63 / 313,433, filed February 24, 2022, and U.S. Provisional Patent Application No. 63 / 401,522, filed August 26, 2022, each of which is incorporated by reference herein in its entirety.

[0002] Described herein is a non-flammable dicationic ionic liquid electrolyte and its synthesis. The electrolyte has a viscosity of 0.01 S cm -1 The use of the non-flammable dicationic ionic liquid electrolyte in various energy storage devices, such as lithium ion batteries, rechargeable batteries, fuel cells, supercapacitors, or solar cells, is also described. [Background technology]

[0003] Energy storage and conversion devices, such as lithium-ion batteries, supercapacitors, solar cells, and fuel cells, have attracted widespread attention over the past decade. Electrolytes play a key role in all of these devices. However, the flammability, low ionic conductivity, and low ionic transport number of existing electrolytes have always been challenges for these products.

[0004] Ionic liquids (ILs) have a melting transition temperature (T m ) below 100°C. In fact, many ILs have typical glass transition temperatures (T g) and melt at temperatures well below ambient. Ionic liquids have potential as functional materials in a variety of emerging areas, including green solvents or green catalysts for chemical reactions, biocatalysis, biopolymer processing, active pharmaceutical ingredients in medicines, and electrolytes for batteries. Multivalent ILs and polyionic liquids, due to their high molecular weight, offer a wider range of physical properties than their monovalent analogues, e.g., higher density, T g ,T m , surface tension and viscosity. This results in better properties, among others, higher thermal stability, better antimicrobial activity, higher capacitance, better performance as stationary phase for gas chromatography, etc. Polyvalent ILs are particularly attractive due to their combination of low viscosity (like conventional ILs) and high ionic conductivity (like polyionic liquids). The properties of polyvalent ILs can be fine-tuned by combining different cations and anions with specific chemical structures that avoid the problem of polydispersity. Currently, polyvalent ILs range from ammonium, phosphonium, imidazolium, pyridinium, pyrrolidinium, piperidinium, triazolium and 4,4'-bipyridinium (viologen) cations. Most of these polyvalent ionic liquids are quaternized S N 2 Menshutkin reaction (quaternization S N 2 It is synthesized via anionic metathesis followed by the Menshutkin reaction.

[0005] There is a need for non-toxic electrolytes that are non-flammable, non-volatile, exhibit high ionic conductivity, high ionic transport number, wide potential window, and have high thermal stability. Summary of the Invention [Means for solving the problem]

[0006] One embodiment described herein is an ionic liquid electrolyte comprising a viologen salt of formula (I).

[0007] [ka] [In the formula,

[0008] R 1 and R 2 are each independently [ka] (wherein n is 3-10),

[0009] m and p are each independently 1 to 3;

[0010] R a If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0011] R b If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0012] [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0013] In one embodiment, m is 1. In another embodiment, p is 1. In another embodiment, m is 2. In another embodiment, p is 2. In another embodiment, the viologen salt of formula (I) is a symmetric viologen salt.

[0014] In another aspect, [ka] are respectively: [ka] It is.

[0015] In another embodiment, the viologen salt of formula (I) is a viologen salt of formula (Ia). [ka]

[0016] In another embodiment, the viologen salt of formula (I) is a viologen salt of formula (Ib). [ka]

[0017] In another embodiment, the viologen salt of formula (I) is [ka] It is.

[0018] Another embodiment described herein is a solid-state battery, a supercapacitor, a solar cell, or a perovskite photovoltaic cell comprising the ionic liquid electrolyte of claim 1. In another aspect, the conductivity of the viologen salt of formula (I) is less than or equal to 0.1 S cm -1 Greater than.

[0019] Another embodiment described herein is an all-solid-state battery comprising: a cathode; an anode; a separator; and an ionic liquid electrolyte, wherein the ionic liquid electrolyte comprises a viologen salt of Formula (I).

[0020] [ka] [In the formula,

[0021] R 1 and R 2 are each independently [ka] where n is 3-10;

[0022] m and p are each independently 1 to 3;

[0023] R a If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0024] R b If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0025] [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0026] Another embodiment described herein is a supercapacitor comprising: a cathode; an anode; a separator; and an ionic liquid electrolyte, wherein the ionic liquid electrolyte comprises a viologen salt of Formula (I).

[0027] [ka] [In the formula,

[0028] R 1 and R 2 are each independently [ka] where n is 3-10;

[0029] m and p are each independently 1 to 3;

[0030] R a If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0031] R b If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0032] [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0033] Another embodiment described herein is a solar cell comprising: an n-type semiconductor layer; a p-type semiconductor layer; and an ionic liquid electrolyte, wherein the ionic liquid electrolyte comprises a viologen salt of Formula (I).

[0034] [ka] [In the formula,

[0035] R 1 and R 2 are each independently [ka] where n is 3-10;

[0036] m and p are each independently 1 to 3;

[0037] R a If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0038] R b If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3OCH2CH3,

[0039] [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0040] Another embodiment described herein is a perovskite photovoltaic cell comprising: an n-type semiconductor layer; an electron transport layer (ETL); a p-type semiconductor layer; and an ionic liquid electrolyte, wherein the ionic liquid electrolyte comprises a viologen salt of Formula (I).

[0041] [ka] [In the formula,

[0042] R 1 and R 2 are each independently [ka] where n is 3-10;

[0043] m and p are each independently 1 to 3;

[0044] R a If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0045] R b If present, independently C 1-4Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0046] [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0047] In one embodiment, m is 1. In another embodiment, p is 1. In another embodiment, m is 2. In another embodiment, p is 2. In another embodiment, the viologen salt is a symmetric viologen salt.

[0048] In another aspect, [ka] are respectively [ka] It is.

[0049] In another embodiment, the viologen salt of formula (I) is a viologen salt of formula (Ia). [ka]

[0050] In another embodiment, the viologen salt of formula (I) is a viologen salt of formula (Ib). [ka]

[0051] In another embodiment, the conductivity of the viologen salt of formula (I) is 0.1 S cm -1 Greater than.

[0052] The patent or application file contains at least one drawing in color. Copies of this patent or patent application publication with color drawing(s) will be provided to the Office upon request and payment of the necessary fee. [Brief description of the drawings]

[0053] [Figure 1] Figures 1A-1E show different cationic structures containing the triflimide anion (Tf)N-, including stilbazolium salts (n=10, 12) (Figure 1B), asymmetric viologens (n=7, 11, 14) (Figure 1C), ionic salts prepared as described herein, 1 (n=1), 2 (n=2), and 3 (n=3) (Figure 1D), and an alkoxy-terminated viologen (Figure 1E). [Diagram 2] Figure 1 shows the DSC thermogram of 1-3 obtained in nitrogen at a heating rate of 10 °C min-1. Upwards indicates exotherm. [Figure 3A] FIG. 1 is a graph showing the dielectric loss modulus ε″ obtained during the isothermal process of 1 upon heating from room temperature (see arrow). [Figure 3B] FIG. 2 is a graph showing the dielectric loss modulus ε″ obtained for two isothermal processes upon heating from room temperature (see arrows). [Figure 3C] Graph showing the dielectric loss modulus ε″ obtained for the isothermal process of 3 upon heating from room temperature (see arrow). [Figure 4A] 1 is a graph showing the real part of the complex conductivity σ' obtained during the isothermal process of 1 upon heating from room temperature (see arrow). [Figure 4B] Graph showing the real part of the complex conductivity σ' obtained for two isothermal processes upon heating from room temperature (see arrows). [Figure 4C] 1 is a graph showing the real part of the complex conductivity σ' obtained during the isothermal process of 3 upon heating from room temperature (see arrow). [Diagram 5] 1 is a graph showing an Arrhenius plot (base 10) of 1-3 corresponding to the DC conductivity σdc inferred from the plateau in the log-log plot of σ' versus frequency. [Figure 6] FIG. 1 shows TGA thermograms of 1, 2 and 3 obtained at a heating rate of 10° C. / min in nitrogen. [Figure 7A] FIG. 1 shows a DSC thermogram of 1 obtained at heating and cooling rates of 10° C. / min in nitrogen. [Figure 7B] FIG. 1 shows the DSC thermogram of 2 obtained at heating and cooling rates of 10° C. / min in nitrogen. [Figure 7C] FIG. 1 shows a DSC thermogram of 3 obtained at heating and cooling rates of 10° C. / min in nitrogen. [Figure 8] FIG. 13 is a graph showing the Cole-Cole plot of 3 at 30° C., 50° C. and 80° C. The AC oscillation voltage was 0.5 V. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0054] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art.For example, the synthetic chemistry techniques described herein and all nomenclature used in connection therewith are known and commonly used in the art.In case of conflict, this disclosure, including definitions, governs.Exemplary methods and materials are described below, but methods and materials similar or equivalent to those described herein can be used to carry out or test the embodiments and aspects described herein.

[0055] As used herein, terms such as "include," "including," "contain," "containing," "having," etc. mean "comprising." The present disclosure also contemplates embodiments that "comprising," "consisting of," and "consisting essentially of" other than the embodiments or components set forth herein, whether or not expressly stated.

[0056] As used herein, the terms "a," "an," "the," and similar terms as used in the context of this disclosure (particularly in the context of the claims) are intended to encompass both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Furthermore, "a," "an," or "the" means "one or more," unless otherwise specified.

[0057] As used herein, the term "or" can mean conjunctive or disjunctive.

[0058] As used herein, the term "substantially" means to a large extent or to a large extent, but not completely.

[0059] As used herein, the term "about" or "approximately" as applied to one or more values ​​of interest refers to a value that is equivalent to a reference value mentioned or that is within an acceptable error range of a particular value as determined by one of ordinary skill in the art, which may depend in part on how the value is measured or determined, such as the limitations of the measurement system. In one aspect, the term "about" refers to any value, including both integer and fractional parts, that is within a variation of up to ±10% of the value to which the term "about" refers. Alternatively, "about" may mean within 3 or more standard deviations, as per the practice of the art. Alternatively, for example, with respect to a biological system or process, the term "about" may mean a value within an order of magnitude, in some embodiments, within 5-fold, and in some embodiments, within 2-fold. As used herein, the symbol "~" means "about" or "approximately."

[0060] All ranges disclosed herein include both limits as discrete values, as well as all integers and decimals specified within the range. For example, a range of 0.1 to 2.0 includes 0.1, 0.2, 0.3, 0.4, ..., 2.0. If a limit is followed by the term "about," the specified range is expanded to include the limit, up to ±10% variation of any value within the range, or within 3 or more standard deviations.

[0061] As used herein, the terms "control" or "reference" are used interchangeably herein. A "reference" or "control" level may be a predetermined value or range, taken as a baseline or benchmark against which a measured result is evaluated. "Control" also refers to a control experiment or control cell.

[0062] Definitions of specific functional groups and chemical terms are described in more detail below.For the purpose of this disclosure, chemical elements are identified according to the Periodic Table of the Elements, CAS edition, Handbook of Chemistry and Physics, 75th Ed., inside cover, and specific functional groups are generally defined as described therein.Furthermore, the general principles of organic chemistry, as well as specific functional sites and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March March's Advanced Organic Chemistry, 5th Edition, John Wiley & Sons, Inc., New York, 2001;Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3rd Edition, Cambridge University Press, Cambridge, 1987, the entire contents of each of which are incorporated herein by reference.

[0063] The term "alkoxy" as used herein refers to an -O-alkyl group. Representative examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, 2-propoxy, butoxy and tert-butoxy.

[0064] As used herein, the term "alkyl" refers to a straight or branched saturated hydrocarbon chain. 1-6 "Alkyl" means a straight or branched hydrocarbon chain containing from 1 to 6 carbon atoms. 1-4"Alkyl" means a straight or branched hydrocarbon chain containing from 1 to 4 carbon atoms. Representative examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0065] The term "alkenyl" as used herein means a straight or branched hydrocarbon chain containing at least one carbon-carbon double bond.

[0066] The term "alkoxyalkyl," as used herein, refers to an alkoxy group, as defined herein, appended to the parent molecular moiety through an alkyl group, as defined herein.

[0067] The term "alkoxyfluoroalkyl" as used herein refers to an alkoxy group, as defined herein, attached to the parent molecular moiety via a fluoroalkyl group, as defined herein. The term "alkylene" as used herein refers to a divalent group derived from a straight or branched hydrocarbon chain of 1 to 10 carbon atoms, for example, 2 to 5 carbon atoms. Representative examples of alkylene include, but are not limited to, -CH2-, -CD2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, and -CH2CH2CH2CH2CH2-.

[0068] The term "alkylamino," as used herein, means that at least one alkyl group, as defined herein, is appended to the parent molecular moiety through an amino group, as defined herein.

[0069] The term "amide" as used herein means -C(O)NR- or -NRC(O)-, where R can be hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, alkenyl, or heteroalkyl.

[0070] The term "aminoalkyl," as used herein, means at least one amino group, as defined herein, is appended to the parent molecular moiety through an alkylene group, as defined herein.

[0071] As used herein, the term "amino" refers to -NR x R y (In the formula, R x and R y may be hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, alkenyl, or heteroalkyl. When an amino is an aminoalkyl group or other moiety that attaches two other moieties together, the amino is represented by -NR x -(In the formula, R x may be hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, alkenyl, or heteroalkyl).

[0072] The term "aryl" as used herein refers to phenyl or a phenyl attached to a parent molecular moiety and fused to a cycloalkane group (e.g., the aryl can be indan-4-yl), a phenyl fused to a 6-membered arene group (i.e., the aryl can be naphthyl), or a phenyl fused to a non-aromatic heterocycle (e.g., the aryl can be benzo[d][1,3]dioxol-5-yl). The term "phenyl" is used to refer to a substituent and the term "6-membered arene" is used to refer to a fused ring. The 6-membered arene is monocyclic (e.g., benzene or benzo). The aryl can be monocyclic (phenyl) or bicyclic (e.g., 9- to 12-membered fused bicyclic systems).

[0073] The term "cyanoalkyl," as used herein, means that at least one --CN group is appended to the parent molecular moiety through an alkylene group, as defined herein.

[0074] The term "cyanofluoroalkyl," as used herein, means that at least one --CN group is appended to the parent molecular moiety through a fluoroalkyl group, as defined herein.

[0075] The term "cycloalkoxy" as used herein refers to a cycloalkyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom.

[0076] The term "cycloalkyl" or "cycloalkane" as used herein refers to a saturated ring system that contains all carbon atoms as ring members and does not contain a double bond. The term "cycloalkyl" is used herein to refer to a cycloalkane that is present as a substituent. Cycloalkyl may be a monocyclic cycloalkyl (e.g., cyclopropyl), a fused bicyclic cycloalkyl (e.g., decahydronaphthalenyl), or a bridged cycloalkyl (e.g., bicyclo[2.2.1]heptanyl) in which two non-adjacent atoms of the ring are connected by an alkylene bridge of 1, 2, 3, or 4 carbon atoms.

[0077] Representative examples of cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, and bicyclo[1.1.1]pentanyl.

[0078] The term "cycloalkenyl" or "cycloalkene" as used herein means a non-aromatic monocyclic or polycyclic ring system containing all carbon atoms as ring members and containing at least one carbon-carbon double bond, preferably having 5 to 10 carbon atoms per ring. The term "cycloalkenyl" is used herein to refer to a cycloalkene present as a substituent. A cycloalkenyl may be a monocyclic cycloalkenyl (e.g., cyclopentenyl), a fused bicyclic cycloalkenyl (e.g., octahydronaphthalenyl), or a bridged cycloalkenyl (e.g., bicyclo[2.2.1]heptenyl) in which two non-adjacent atoms of the ring are connected by an alkylene bridge of 1, 2, 3, or 4 carbon atoms.

[0079] Examples of monocyclic cycloalkenyl rings include cyclopentenyl, cyclohexenyl, or cycloheptenyl. Examples of monocyclic cycloalkenyl rings include cyclopentenyl, cyclohexenyl, or cycloheptenyl.

[0080] The term "carbocyclyl" means "cycloalkyl" or "cycloalkenyl." The term "carbocycle" means "cycloalkane" or "cycloalkene." The term "carbocyclyl" refers to a "carbon ring" present as a substituent.

[0081] The terms "cycloalkylene" and "heterocyclylene" refer to a divalent group derived from a base ring, i.e., a cycloalkane, a heterocycle. Illustrative examples of cycloalkylene and heterocyclylene include, respectively: [ka] Cycloalkylene and heterocyclylene include 1,1-C 3-6 Cycloalkylene (i.e. [ka] ) and other geminal divalent groups. A further example is 1,1-cyclopropylene (i.e., [ka] ) are mentioned.

[0082] The term "fluoroalkyl" as used herein means an alkyl group, as defined herein, in which one, two, three, four, five, six, seven, or eight hydrogen atoms are replaced by fluorine. Representative examples of fluoroalkyl include, but are not limited to, 2-fluoroethyl, 2,2,2-trifluoroethyl, trifluoromethyl, difluoromethyl, pentafluoroethyl, and trifluoropropyl, such as 3,3,3-trifluoropropyl.

[0083] The term "fluoroalkylene" as used herein means an alkylene group, as defined herein, in which one, two, three, four, five, six, seven, or eight hydrogen atoms are replaced by fluorine. Representative examples of fluoroalkyl include, but are not limited to, -CF2-, -CH2CF2-, 1,2-difluoroethylene, 1,1,2,2-tetrafluoroethylene, 1,3,3,3-tetrafluoropropylene, 1,1,2,3,3-pentafluoropropylene, and perfluoropropylenes such as 1,1,2,2,3,3-hexafluoropropylene.

[0084] The term "halogen" or "halo" as used herein means Cl, Br, I, or F.

[0085] The term "haloalkyl" as used herein means an alkyl group, as defined herein, in which 1, 2, 3, 4, 5, 6, 7, or 8 hydrogen atoms are replaced with halogen.

[0086] The term "haloalkoxy," as used herein, means at least one haloalkyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom.

[0087] The term "halocycloalkyl" as used herein means a cycloalkyl group, as defined herein, in which one or more hydrogen atoms are replaced with halogen.

[0088] The term "heteroalkyl" as used herein means an alkyl group, as defined herein, in which one or more carbon atoms are replaced with a heteroatom selected from S, O, P, and N. Representative examples of heteroalkyls include, but are not limited to, alkyl ethers, secondary alkyl amines, tertiary alkyl amines, amides, and alkyl sulfides.

[0089] The term "heteroaryl" as used herein refers to an aromatic monocyclic heteroatom-containing ring (monocyclic heteroaryl) or a bicyclic ring system (bicyclic heteroaryl) that contains at least one monocyclic heteroaromatic ring. The term "heteroaryl" is used herein to refer to a heteroarene present as a substituent. A monocyclic heteroaryl is a 5- or 6-membered ring that contains at least one heteroatom independently selected from the group consisting of N, O, and S (e.g., 1, 2, 3, or 4 heteroatoms independently selected from O, S, and N). A 5-membered aromatic monocyclic ring has 2 double bonds, and a 6-membered aromatic monocyclic ring has 3 double bonds. Bicyclic heteroaryls are 8- to 12-membered ring systems, including fused bicyclic heteroaromatic ring systems (i.e., 10π electron systems), such as monocyclic heteroaryl rings fused to 6-membered arenes (e.g., quinolin-4-yl, indol-1-yl), monocyclic heteroaryl rings fused to monocyclic heteroarenes (e.g., naphthyridinyl), and phenyls fused to monocyclic heteroarenes (e.g., quinolin-5-yl, indol-4-yl). Bicyclic heteroaryl / heteroarene groups include fused bicyclic heteroaromatic ring systems that are 9-membered rings with 4 double bonds and at least one heteroatom that donates a lone pair to the fully aromatic 10π electron system, such as ring systems with a nitrogen atom at the ring junction (e.g., imidazopyridine) or benzoxadiazolyl. Bicyclic heteroaryl also includes fused bicyclic ring systems composed of one heteroaromatic ring and one non-aromatic ring, such as a monocyclic heteroaryl ring fused to a monocyclic carbocycle (e.g., 6,7-dihydro-5H-cyclopenta[b]pyridinyl) or a monocyclic heteroaryl ring fused to a monocyclic heterocycle (e.g., 2,3-dihydrofuro[3,2-b]pyridinyl). A bicyclic heteroaryl is attached to the parent molecular moiety at an aromatic ring atom.Other representative examples of heteroaryl include indolyl (e.g., indol-1-yl, indol-2-yl, indol-4-yl), pyridinyl (including pyridin-2-yl, pyridin-3-yl, pyridin-4-yl), pyrimidinyl, pyrazinyl, pyridazinyl, pyrazolyl (e.g., pyrazol-4-yl), pyrrolyl, benzopyrazolyl, 1,2,3-triazolyl (e.g., triazol-4-yl), 1,3,4-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-oxadiazolyl, 1,2,4-oxadiazolyl, imidazolyl, thiazolyl (e.g., thiazol-4-yl), isothiazolyl, thienyl, benzimidazolyl (e.g., benzimidazolyl, Examples of aryl groups include, but are not limited to, benzothiazolyl, benzoxazolyl, benzoxadiazolyl, benzothienyl, benzofuranyl, isobenzofuranyl, furanyl, oxazolyl, isoxazolyl, purinyl, isoindolyl, quinoxalinyl, indazolyl (e.g., indazol-4-yl, indazol-5-yl), quinazolinyl, 1,2,4-triazinyl, 1,3,5-triazinyl, isoquinolinyl, quinolinyl, imidazo[1,2-a]pyridinyl (e.g., imidazo[1,2-a]pyridin-6-yl), naphthyridinyl, pyridoimidazolyl, thiazolo[5,4-b]pyridin-2-yl, and thiazolo[5,4-d]pyrimidin-2-yl.

[0090] The term "heterocycle" or "heterocyclic" as used herein means a monocyclic heterocycle, a bicyclic heterocycle, or a tricyclic heterocycle. The term "heterocyclyl" is used herein to refer to a heterocycle present as a substituent. The monocyclic heterocycle is a 3-, 4-, 5-, 6-, 7-, or 8-membered ring containing at least one heteroatom independently selected from the group consisting of O, N, and S. The 3- or 4-membered ring contains 0 or 1 double bond and 1 heteroatom selected from the group consisting of O, N, and S. The 5-membered ring contains 0 or 1 double bond and 1, 2, or 3 heteroatoms selected from the group consisting of O, N, and S. The 6-membered ring contains 0, 1, or 2 double bonds and 1, 2, or 3 heteroatoms selected from the group consisting of O, N, and S. The 7- and 8-membered rings contain 0, 1, 2, or 3 double bonds and 1, 2, or 3 heteroatoms selected from the group consisting of O, N, and S. Representative examples of monocyclic heterocyclyls include azetidinyl, azepanyl, aziridinyl, diazepanyl, 1,3-dioxanyl, 1,3-dioxolanyl, 1,3-dithiolanyl, 1,3-dithianyl, imidazolinyl, imidazolidinyl, isothiazolinyl, isothiazolidinyl, isoxazolinyl, isoxazolidinyl, morpholinyl, 2-oxo-3-piperidinyl, 2-oxoazepan-3-yl, oxadiazolinyl, oxadiazolidinyl, oxazolinyl, oxazolidinyl, oxetanyl, oxepan ... These include, but are not limited to, oxocanyl, piperazinyl, piperidinyl, pyranyl, pyrazolinyl, pyrazolidinyl, pyrrolinyl, pyrrolidinyl, tetrahydrofuranyl, tetrahydropyranyl, tetrahydropyridinyl, tetrahydrothienyl, thiadiazolinyl, thiadiazolidinyl, 1,2-thiazinanyl, 1,3-thiazinanyl, thiazolinyl, thiazolidinyl, thiomorpholinyl, 1,1-dioxidothiomorpholinyl (thiomorpholinesulfone), thiopyranyl, and trithianyl.A bicyclic heterocycle is a monocyclic heterocycle fused to a 6-membered arene, or a monocyclic heterocycle fused to a monocyclic cycloalkane, or a monocyclic heterocycle fused to a monocyclic cycloalkene, or a monocyclic heterocycle fused to a monocyclic heterocycle, or a monocyclic heterocycle fused to a monocyclic heteroarene, or a spiroheterocyclic group, or a bridged monocyclic heterocyclic ring system in which two non-adjacent atoms of the ring are linked by an alkylene bridge of 1, 2, 3, or 4 carbon atoms, or an alkenylene bridge of 2, 3, or 4 carbon atoms. A bicyclic heterocyclyl is attached to the parent molecular moiety at a non-aromatic ring atom (e.g., indolin-1-yl). Representative examples of bicyclic heterocyclyls include chroman-4-yl, 2,3-dihydrobenzofuran-2-yl, 2,3-dihydrobenzothien-2-yl, 1,2,3,4-tetrahydroisoquinolin-2-yl, 2-azaspiro[3.3]heptan-2-yl, 2-oxa-6-azaspiro[3.3]heptan-6-yl, azabicyclo[2.2.1]heptyl (including 2-azabicyclo[2.2.1]hept-2-yl), and azabicyclo[3.1.0]hexanyl (including 3-azabicyclo[3.1.0]hexan-3-yl). , 2,3-dihydro-1H-indol-1-yl, isoindolin-2-yl, octahydrocyclopenta[c]pyrrolyl, octahydropyrrolopyridinyl, tetrahydroisoquinolinyl, 7-oxabicyclo[2.2.1]heptanyl, hexahydro-2H-cyclopenta[b]furanyl, 2-oxaspiro[3.3]heptanyl, 3-oxaspiro[5.5]undecanyl, 6-oxaspiro[2.5]octan-1-yl, and 3-oxabicyclo[3.1.0]hexan-6-yl. Tricyclic heterocycles are exemplified by bicyclic heterocycles fused to a 6-membered arene, or a bicyclic heterocycle fused to a monocyclic cycloalkane, or a bicyclic heterocycle fused to a monocyclic cycloalkene, or a bicyclic heterocycle fused to a monocyclic heterocycle, or a bicyclic heterocycle in which two non-adjacent atoms of the bicyclic ring are linked by an alkylene bridge of 1, 2, 3, or 4 carbon atoms, or an alkenylene bridge of 2, 3, or 4 carbon atoms.Examples of tricyclic heterocycles include, but are not limited to, octahydro-2,5-epoxypentalene, hexahydro-2H-2,5-methanocyclopenta[b]furan, hexahydro-1H-1,4-methanocyclopenta[c]furan, aza-adamantane (1-azatricyclo[3.3.1.13,7]decane), and oxa-adamantane (2-oxatricyclo[3.3.1.13,7]decane). Monocyclic, bicyclic, and tricyclic heterocyclyls are attached to the parent molecular moiety through a non-aromatic ring atom.

[0091] The term "hydroxyl" or "hydroxy" as used herein refers to an --OH group.

[0092] The term "hydroxyalkyl," as used herein, means at least one --OH group, appended to the parent molecular moiety through an alkylene group, as defined herein.

[0093] The term "hydroxyfluoroalkyl," as used herein, means at least one --OH group, appended to the parent molecular moiety through a fluoroalkyl group, as defined herein.

[0094] Terms such as "alkyl," "cycloalkyl," "alkylene," etc., may in a particular case be preceded by a designation indicating the number of atoms present in the group (e.g., "C 1-4 Alkyl, C 3-6 Cycloalkyl, C 1-4 These definitions are used as commonly understood by those of ordinary skill in the art. For example, a "C" followed by a subscript number indicates the number of carbon atoms present in the following group. Thus, a "C alkyl" is an alkyl group having 3 carbon atoms (i.e., n-propyl, isopropyl). 1-4 When a range is given, such as "C", the subsequent group may have any number of carbon atoms within the recited range. 1-4 "Alkyl" refers, for example, to an alkyl group having from 1 to 4 carbon atoms, but in different arrangements (ie, straight or branched).

[0095] The term "substituted" refers to a group that may be further substituted with one or more non-hydrogen substituents. Substituents include, but are not limited to, halogen, =O (oxo), =S (thioxo), cyano, nitro, fluoroalkyl, alkoxyfluoroalkyl, fluoroalkoxy, alkyl, alkenyl, alkynyl, haloalkyl, haloalkoxy, heteroalkyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, heterocycle, cycloalkylalkyl, heteroarylalkyl, arylalkyl, hydroxy, hydroxyalkyl, alkoxy, alkoxyalkyl, alkylene, aryloxy, phenoxy, benzyloxy, amino, alkylamino, acylamino, aminoalkyl, arylamino, sulfonylamino, sulfinylamino, sulfonyl, alkylsulfonyl, arylsulfonyl, aminosulfonyl, sulfinyl, -COOH, ketone, amide, carbamate, and acyl.

[0096] This specification includes high ionic conductivity (>0.01 S cm -1 A non-flammable dicationic ionic liquid electrolyte is described for use in electrical energy storage and conversion devices, such as lithium-ion batteries, fuel cells, solar cells, and supercapacitors, that exhibits high ionic transport numbers (>0.5) and a wide potential window (>6 V). Existing electrolytes, both based on conventional organic liquids and ionic liquids, all exhibit low thermal conductivity (>100 s), high ionic transport numbers (>0.5), and a wide potential window (>6 V). -4 S cm -1 From 10 -2 S cm -1 It exhibits ionic conductivity in the range of 0.1 to 1.0 and is highly flammable.

[0097] The electrolytes described herein exhibit high ionic conductivity and are non-flammable.

[0098] In some embodiments, the ionic liquids described herein can also be used as green solvents or green catalysts for chemical reactions, biocatalysis, biopolymer processing, and active pharmaceutical ingredients in medicines.

[0099] In some embodiments, dicationic ionic liquid electrolytes are achieved by employing an extended core structure containing oxyethylene termini along with a suitable combined organic cation and organic / inorganic anion salt (e.g., triflimide viologen).

[0100] In some embodiments, these multivalent ionic liquids and polyion gels can be synthesized via the Zincke reaction.

[0101] The embodiments described herein exhibit the following characteristics: High ionic conductivity (>0.01S cm -1 ); high ion transport number (>0.5); non-flammable; high thermal stability; non-toxic; sustainable; liquid nature below 100°C; wide potential window; and non-LC (liquid crystal) nature.

[0102] In some embodiments, suitable ammonium, phosphonium, imidazolium, pyridinium, pyrrolidinium, piperidinium, triazolium, 4,4'-bipyridinium and alkoxy terminated viologen cations can be used.

[0103] In some embodiments, extended oxyethylene ends (with n varying from 1 to 15; FIG. 1) can be used.

[0104] In some embodiments, the ionic liquid may have a melting transition temperature of less than 100°C and a glass transition temperature of between -93°C and -53°C.

[0105] In some embodiments, these ionic liquids can exhibit high thermal stability (see FIG. 5).

[0106] In some embodiments, these ionic liquids are amorphous in nature and inhibit crystallization.

[0107] In some embodiments, the conductivity is increased by extending the oxyethylene ends.

[0108] In some embodiments, these ionic liquids may exhibit low temperature dependent conductivity.

[0109] In some embodiments, the longer oxyethylene ends act as plasticizers.

[0110] In some embodiments, the longer oxyethylene ends facilitate ionic movement at the ends due to their conductivity.

[0111] In some embodiments, these ionic liquids may exhibit a wide potential window (>6V).

[0112] One embodiment described herein is an ionic liquid electrolyte comprising a viologen salt of formula (I).

[0113] [ka] [In the formula,

[0114] R 1 and R 2 are each independently [ka] where n is 3-10;

[0115] m and p are each independently 1 to 3;

[0116] R a If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0117] R b If present, independently C1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0118] [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0119] In one embodiment, m is 1. In another embodiment, p is 1. In another embodiment, m is 2. In another embodiment, p is 2. In another embodiment, the viologen salt of formula (I) is a symmetric viologen salt.

[0120] In another aspect, [ka] are respectively [ka] It is.

[0121] In another embodiment, the viologen salt of formula (I) is a viologen salt of formula (Ia). [ka]

[0122] In another embodiment, the viologen salt of formula (I) is a viologen salt of formula (Ib). [ka]

[0123] In another embodiment, the viologen salt of formula (I) is [ka] It is.

[0124] Another embodiment described herein is an all-solid-state battery, a supercapacitor, a solar cell, or a perovskite photovoltaic cell comprising the ionic liquid electrolyte of claim 1. In another aspect, the conductivity of the viologen salt of formula (I) is less than 0.1 S cm -1 Greater than.

[0125] Another embodiment described herein is an all-solid-state battery comprising: a cathode; an anode, a separator; and an ionic liquid electrolyte, wherein the ionic liquid electrolyte comprises a viologen salt of Formula (I).

[0126] [ka] [In the formula,

[0127] R 1 and R 2 are each independently [ka] where n is 3-10;

[0128] m and p are each independently 1 to 3;

[0129] R a If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0130] R b If present, independently C 1-4Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0131] [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0132] Another embodiment described herein is a supercapacitor comprising: a cathode; an anode; a separator; and an ionic liquid electrolyte, wherein the ionic liquid electrolyte comprises a viologen salt of Formula (I).

[0133] [ka] [In the formula,

[0134] R 1 and R 2 are each independently [ka] where n is 3-10;

[0135] m and p are each independently 1 to 3;

[0136] R a If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3OCH2CH3,

[0137] R b If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3, [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0138] Another embodiment described herein is a solar cell comprising: an n-type semiconductor layer; a p-type semiconductor layer; and an ionic liquid electrolyte, wherein the ionic liquid electrolyte comprises a viologen salt of Formula (I).

[0139] [ka] [In the formula,

[0140] R 1 and R 2 are each independently [ka] where n is 3-10;

[0141] m and p are each independently 1 to 3;

[0142] R a If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0143] R b If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0144] [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0145] Another embodiment described herein is a perovskite photovoltaic cell comprising: an n-type semiconductor layer; an electron transport layer (ETL); a p-type semiconductor layer; and an ionic liquid electrolyte, wherein the ionic liquid electrolyte comprises a viologen salt of Formula (I).

[0146] [ka] [In the formula,

[0147] R 1 and R 2 are each independently [ka] where n is 3-10;

[0148] m and p are each independently 1 to 3;

[0149] R a If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0150] R b If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0151] [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0152] In one embodiment, m is 1. In another embodiment, p is 1. In another embodiment, m is 2. In another embodiment, p is 2. In another embodiment, the viologen salt is a symmetric viologen salt.

[0153] In another aspect, [ka] are respectively [ka] It is.

[0154] In another embodiment, the viologen salt of formula (I) is a viologen salt of formula (Ia). [ka]

[0155] In another embodiment, the viologen salt of formula (I) is a viologen salt of formula (Ib). [ka]

[0156] In another embodiment, the conductivity of the viologen salt of formula (I) is 0.1 S cm -1 Greater than.

[0157] It will be apparent to those skilled in the relevant art that suitable modifications and adaptations to the compositions, formulations, methods, steps, and applications described herein may be made without departing from the scope of any embodiment or aspect thereof. The compositions and methods provided are exemplary and are not intended to limit the scope of any embodiment described. All of the various embodiments, aspects, and options disclosed herein may be combined in any variation or iteration. The scope of the compositions, formulations, methods, and processes described herein includes all actual or potential combinations of the embodiments, aspects, options, examples, and preferences described herein. The exemplary compositions and formulations described herein may omit any component, may substitute any component disclosed herein, or may include any component disclosed elsewhere herein. The ratio of the mass of any component of the compositions or formulations disclosed herein to the mass of any other component in the formulation or to the total mass of other components in the formulation is disclosed herein as if expressly disclosed. The meaning of any term in any of the patents or publications incorporated by reference shall be governed by the meaning of the term or expression in this disclosure if it conflicts with the meaning of the term used in this disclosure. Moreover, the foregoing discussion discloses and describes merely exemplary embodiments. All patents and publications cited herein are hereby incorporated by reference for their specific teachings.

[0158] Various embodiments and aspects of the invention described herein are summarized by the following subsections:

[0159] Item 1. An ionic liquid electrolyte comprising a viologen salt of formula (I). [ka] [In the formula,

[0160] R 1 and R 2 are each independently [ka] where n is 3-10;

[0161] m and p are each independently 1 to 3;

[0162] R a If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0163] R b If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0164] [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0165] Item 2. 2. The ionic liquid electrolyte according to item 1, wherein m is 1.

[0166] Item 3. 2. The ionic liquid electrolyte according to item 1, wherein p is 1.

[0167] Item 4. 2. The ionic liquid electrolyte according to item 1, wherein m is 2.

[0168] Item 5. Item 2. The ionic liquid electrolyte according to item 1, wherein p is 2.

[0169] Item 6. 2. The ionic liquid electrolyte according to item 1, wherein the viologen salt of formula (I) is a symmetric viologen salt.

[0170] Item 7. [ka] are respectively, [ka] 2. The ionic liquid electrolyte according to item 1,

[0171] Item 8. 2. The ionic liquid electrolyte according to item 1, wherein the viologen salt of formula (I) is a viologen salt of formula (Ia). [ka]

[0172] Item 9. 2. The ionic liquid electrolyte according to item 1, wherein the viologen salt of formula (I) is a viologen salt of formula (Ib). [ka]

[0173] Item 10. The viologen salt of formula (I) [ka] 2. The ionic liquid electrolyte according to item 1,

[0174] Item 11. Item 1. An all-solid-state battery, a supercapacitor, a solar cell, or a perovskite photovoltaic cell comprising the ionic liquid electrolyte according to item 1.

[0175] Item 12. The conductivity of the viologen salt of formula (I) is 0.1 S cm -1 2. The ionic liquid electrolyte according to claim 1, wherein

[0176] Item 13. Cathode; anode; separator; and An all-solid-state battery comprising an ionic liquid electrolyte, The all-solid-state battery, wherein the ionic liquid electrolyte comprises a viologen salt of formula (I).

[0177] [ka] [In the formula,

[0178] R 1 and R 2 are each independently [ka] where n is 3-10;

[0179] m and p are each independently 1 to 3;

[0180] R a If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0181] R b If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3OCH2CH3,

[0182] [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0183] Item 14. Cathode; anode; separator; and 1. A supercapacitor comprising an ionic liquid electrolyte, A supercapacitor wherein the ionic liquid electrolyte comprises a viologen salt of formula (I).

[0184] [ka] [In the formula,

[0185] R 1 and R 2 are each independently [ka] where n is 3-10;

[0186] m and p are each independently 1 to 3;

[0187] R a If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0188] Rb If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0189] [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0190] Item 15. n-type semiconductor layer; A p-type semiconductor layer; and Ionic Liquid Electrolytes A solar cell comprising: A solar cell, wherein the ionic liquid electrolyte comprises a viologen salt of formula (I).

[0191] [ka] [In the formula,

[0192] R 1 and R 2 are each independently [ka] where n is 3-10;

[0193] m and p are each independently 1 to 3;

[0194] R a If present, independently C 1-4 Alkyl, C 1-2Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0195] R b If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0196] [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0197] Item 16. n-type semiconductor layer; Electron transport layer (ETL); A p-type semiconductor layer; and Ionic Liquid Electrolytes A perovskite photovoltaic cell comprising: 2. A perovskite photovoltaic cell, wherein the ionic liquid electrolyte comprises a viologen salt of formula (I).

[0198] [ka] [In the formula,

[0199] R 1 and R 2 are each independently [ka] where n is 3-10;

[0200] m and p are each independently 1 to 3;

[0201] R a If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0202] R b If present, independently C 1-4 Alkyl, C 1-2 Haloalkyl, -OC 1-4 Alkyl, -OC 1-2 Haloalkyl, halogen, -NO2, -CN, or -(OCH2CH2) 1-3 OCH2CH3,

[0203] [ka] are respectively: [ka] (Wherein, R' is -(OCH2CH2) 1-10 OCH2CH3) is]

[0204] Item 17. 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell according to any one of items 13 to 16, wherein m is 1.

[0205] Item 18. 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell according to any one of items 13 to 16, wherein p is 1.

[0206] Item 19. 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell according to any one of items 13 to 16, wherein m is 2.

[0207] Item 20. 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell according to any one of items 13 to 16, wherein p is 2.

[0208] Item 21. 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell according to any one of items 13 to 16, wherein the viologen salt is a symmetric viologen salt.

[0209] Item 22. [ka] are respectively, [ka] 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell according to any one of items 13 to 16,

[0210] Item 23. 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell according to any one of items 13 to 16, wherein the viologen salt of formula (I) is a viologen salt of formula (Ia). [ka]

[0211] Item 24. 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell according to any one of items 13 to 16, wherein the viologen salt of formula (I) is a viologen salt of formula (Ib). [ka]

[0212] Item 25. The conductivity of the viologen salt of formula (I) is 0.1 S cm -1 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell according to any one of items 13 to 16, wherein the total mass of the all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell is greater than or equal to 1000 nm. EXAMPLES

[0213] material and method All chemicals and solvents were reagent grade and were purchased from commercial vendors (Acros Organics, Alfa-Aesar, Sigma-Aldrich, and TCI America) and used as received. FTIR spectra were recorded on a Shimadzu infrared spectrometer. Salt samples were prepared by thin film casting from chloroform onto NaCl plates, followed by drying in vacuum at 70 °C overnight.

[0214] Elongated viologen salts 1 to 3 1 H, 13 C and 19 F nuclear magnetic resonance (NMR) sample solutions were prepared by dissolving 10 mg of each salt in 1 mL of CD3OD, and spectra were recorded at room temperature using a VNMR 400 spectrometer operating at 400 MHz, 100 MHz, and 376 MHz, respectively, with chemical shifts of 1 H nuclei and 13 For C nuclei, tetramethylsilane (TMS) 19 The F nucleus was referenced to trichlorofluoromethane (CFCl3). Elemental analyses were performed by Atlantic Microlab Inc. (Norcross, GA).

[0215] The phase transition temperature of the compound was measured using a TA module differential scanning calorimeter DSC Q200 series at 10°C min in nitrogen. -1 The temperature axis of the DSC thermogram was calibrated with high purity indium and tin reference standards. The thermal stability characteristics of the compounds were characterized in nitrogen at a heating and cooling rate of 10 °C min-1 The phase transitions were observed between crossed polarizers on an Olympus BX51 microscope.

[0216] For dielectric and conductivity analyses, the triflimide salt was sandwiched between two stainless steel electrodes (top and bottom electrodes with diameters of 10 and 20 mm, respectively) separated by a 120 μm diameter fused silica fiber spacer. The temperature of the sample was controlled using a Lakeshore temperature controller. Dielectric measurements were performed over the frequency range of 0.01 Hz to 10 6 The measurements were performed using a lab-built dielectric spectrometer at 1000 Hz. Temperatures were measured at 5°C intervals between -50°C and 40°C. For each measurement, the sample was allowed to stabilize at a particular temperature for approximately 2 minutes.

[0217] Synthesis procedure for 4-oligoethyleneoxyaniline 4-(2-Ethoxyethoxy)aniline and 4-(2-(2-ethoxyethoxy)ethoxy]aniline and 4-(2-(2-(2-ethoxyethoxy)ethoxy)ethoxy]aniline were prepared according to the procedure of Sudhakar et al., Liq.Cryst. 27 1525-1532 (2000) with some modifications. The modifications were the use of acetone instead of ethanol in the alkylation of 4-hydroxyacetanilide and oligoethylene bromide instead of oligoethylene tosylate. The oligoethylene bromide was prepared via the Appel reaction (step 1). Sudhakar et al., Liq.Cryst. 27 1525-1532 (2000). The synthesis of 4-[2-[2-(2-ethoxyethoxy)ethoxy)ethoxy]ethoxy]aniline is described in detail below. The other two 4-oligoethyleneoxyanilines were prepared in the same manner. 4-[2-[2-(2-ethoxyethoxy)ethoxy)ethoxy]aniline was prepared in a three-step reaction starting with the bromine addition reaction of 4-[2-(2-ethoxyethoxy)ethoxy]ethanol via the Appel reaction. Kim et al., J. Med. Chem. 50:5217-5226 (2007). The synthesis of 4-[2-(2-ethoxyethoxy)ethoxy]bromide is as follows: A given amount of 4-[2-(2-ethoxyethoxy)ethoxy]ethanol (1.000 g, 5.61 mmol) and excess amount of triphenylphosphine (2.458 g, 9.37 mmol) were added to an Erlenmeyer flask and dissolved in 10 mL of dichloromethane (DCM). The mixture was stirred and cooled to 0° C., and carbon tetrabromide (2.326 g, 7.01 mmol) dissolved in 10 mL of DCM was added dropwise to the mixture. After all the carbon tetrabromide solution was added, the reaction mixture was stirred at room temperature for 30 minutes. After 30 minutes, the DCM was removed using a rotary evaporator. Immediately after the DCM was removed, 30 mL of hexane was added to the reaction mixture to precipitate the excess starting material and by-products. The reaction mixture in hexane was cooled to −77° C. by keeping the flask in a bath of isopropyl alcohol and dry ice.The contents of the flask were filtered through Celite and the hexane was evaporated to leave the pure product 4-[2-(2-ethoxyethoxy)ethoxy]ethyl bromide (0.700 g, 2.90 mmol, yield=52%).

[0218] In step 2, alkylation of 4-hydroxyacetanilide was carried out as follows: 4-[2-(2-ethoxyethoxy)ethoxy]bromide (0.700 g, 2.90 mmol) was added to a round bottom flask containing 4-hydroxyacetanilide (0.483 g, 3.19 mmol) dissolved in 50 mL of acetone. Potassium carbonate (0.401 mg, 2.90 mmol) was added to the flask and the reaction mixture was heated to reflux with stirring for 24 h. Once the reaction had stopped, the mixture was allowed to cool to room temperature and filtered. Acetone was removed using a rotary evaporator and the product was purified by extraction with DCM and warm deionized water. The DCM was then evaporated to give the pure product 4-[2-[2-(2-ethoxyethoxy)ethoxy]ethoxy]acetanilide (0.800 g, 2.57 mmol, yield=88%).

[0219] Finally, the hydrolysis reaction (step 2) was carried out by adding 4-[2-[2-(2-ethoxyethoxy)ethoxy]ethoxy]acetanilide (0.800 g, 2.57 mmol) to a three-neck flask containing sodium hydroxide (2.000 g, 50.0 mmol) dissolved in 25 mL of deionized water. The reaction flask was heated under nitrogen atmosphere for 12 h. Once the reaction had stopped, the flask was cooled to room temperature and the desired product was purified by extraction with DCM and deionized water. The DCM was removed using a rotary evaporator to give the pure product 4-[2-[2-(2-ethoxyethoxy)ethoxy]ethoxy]aniline (0.576 g, 2.14 mmol, yield = 83%).

[0220] Synthesis procedure for Zincke Salt The Zinke salt was prepared (step 3) by reaction of 4,4'-bipyridine (1 equiv.) with 1-chloro-2,4-dinitrobenzene (2.5 equiv.) in acetonitrile under heating according to the literature: Sharma et al., Synth. Met. 106:97-105 (1999); Cheng and Kurth, Org. Prep. Proced. Int. 34:585-608 (2002).

[0221] [ka]

[0222] Synthetic procedures for bis-(4-oligoethyleneoxyphenyl)-4,4'-bipyridinium dichlorides (P1 to P3). The synthesis of P2 is shown as an example (step 4). P1 and P3 were prepared by the same procedure. P2 was prepared by adding 4-(2-(2-ethoxyethoxy)ethoxy]aniline (0.192 g, 0.85 mmol) to a round-bottom flask containing Zinke salt (0.217 g, 0.39 mmol) and 15 mL of N,N-dimethylacetamide (DMAc). The reaction mixture was stirred at room temperature for 3 h. Once the reaction was stopped, the crude product was easily collected by gravity filtration and washed with acetone to give the pure product (0.162 g, 0.25 mmol).

[0223] Data for P1: Yield 93%. δH(CD3OD,400MHz,ppm):9.50(4H,d,J=6.8),8.89(4H,d,J=6.8),7.89(4H ,d,J=9.2),7.34(4H,d,J=9.2),4.30(4H,t,J=4.4),3.87(4H,t,J=2.8),3. 65(4H,t,J=6.8),1.25(6H,t,J=7.2).δC(CD3OD,100MHz,ppm):163.18,151 .17,146.82,137.02,128.30,126.94,117.44,69.95,69.53,67.85,15.47.

[0224] Data for P2: Yield 65%. δH(CD3OD,400MHz,ppm):9.50(4H,br),8.88(4H,br),7.88(4H,d,J=8.4),7.34(4H,d ,J=8.8),4.31(4H,t,J=4.4),3.92(4H,t,J=2.8),3.73(4H,t,J=4.4),3.64(4H,t,J=2 .8),3.58(4H,t,J=6.8),1.21(6H,t,J=6.8).δC(CD3OD,100MHz,ppm):163.19,151.18 ,146.83,137.00,128.28,126.93,117.46,71.85,70.95,70.62,69.53,67.64,15.47.

[0225] Data for P3: Yield 70%. δH(CD3OD,400MHz,ppm):9.50(4H,d,J=6.4),8.88(4H,d,J=6.4),7.88(4H,d,J=8.8) ,7.34(4H,d,J=9.2),4.31(4H,t,J=4.8),3.93(4H,t,J=3.2),3.75(4H,t,J=4.0),3.5 1-3.69(16H,m),1.20(6H,t,J=6.8).δC(CD3OD,100MHz,ppm):163.19,151.18,146.8 3,137.01,128.28,126.94,117.46,71.84,71.64,70.94,70.62,69.55,67.59,15.48.

[0226] Synthetic Procedure for Bis-(4-oligoethyleneoxyphenyl)-4,4'-bipyridinium bis(triflimides) 1 to 3 via Metathesis Reaction Salt 3 was synthesized from salt 1 via metathesis reaction of the dichloride salt with lithium triflimide. The synthesis of 2 is shown as an example (step 5). 1 and 3 were prepared by the same method. The lithium salt (0.316 g, 1.10 mmol) dissolved in 5 mL of deionized water was added to a reaction flask containing a clear solution of P2 (0.284 g, 0.44 mmol) dissolved in 20 mL of ethanol. The flask was heated to reflux for 72 h. Once the reaction had stopped, the solvent ethanol was removed using a rotary evaporator. The reaction mixture was then dissolved in chloroform and extracted from deionized water to give a clean brown product (0.466 g, 0.41 mmol).

[0227] Data for 1: FTIR (NaCl, v max cm -1 ):3117,3071,2978,2932,2870,1628,1597,1450,1342,1180,1126,1049,826,787,733,610,571,501. Yield 70%. δH(CD3OD,400MHz,ppm):9.46(4H,br),8.81(4H,br),7.84(4H,d,J=8.4),7.33(4 H,d,J=9.2),4.29(4H,t,J=4.8),3.87(4H,t,J=2.8),3.65(4H,t,J=7.2),1.25(6H ,t,J=7.2).δC(CD3OD,100MHz,ppm):163.20,146.83,128.27,126.91,122.77,119 .58,117.44,69.95,69.52,67.86,15.46.δF(CD3OD,376MHz,ppm):-80.14.Elemental analysis:C 34 H 34 F 12 N4O 12 Calculated value of S4 (1046.89): C, 39.01; H, 3.27; N, 5.35; S, 12.25%. Measured values: C, 39.17; H, 3.19; N, 5.46; S, 12.25%.

[0228] Data for 2: FTIR (NaCl, v max cm -1): 3125, 3071, 2978, 2932, 2878, 1636, 1597, 1543, 1504, 1450, 1427, 1350, 1258, 1196, 1134, 1096, 1057, 941, 833, 795, 741, 610, 571, 509. Yield 93%. δH(CD3OD, 400 MHz, ppm): 9.47 (4H, d, J = 5.6), 8.82 (4H, d, J = 5.6), 7.85 (4H, d, J = 8.8), 7.34 (4H, d, J = 9.2), 4.31 (4H, t, J = 4.4), 3.93 (4H, t, J = 4.4), 3.74 (4H, t, J = 4.4), 3.64 (4H, t, J = 6.0), 3.58 (4H, t, J = 7.2), 1.22 (6H, t, J = 6.8). δC(CD3OD, 100 MHz, ppm): 163.19, 151.31, 146.83, 136.98, 128.26, 126.90, 122.76, 119.58, 117.45, 71.83, 70.94, 70.60, 69.50, 67.63, 15.46. δF(CD3OD, 376 MHz, ppm): -80.44. Elemental analysis: C 38 H 42 F 12 N4O 14 Calculated values for C

[0229] 3 data: FTIR(NaCl, v max cm -1):3117,3071,2878,1636,1597,1504,1450,1350,1258,1188,1134,1057,949,833,787,741,648,610,571,501. Yield 89%. δH(CD3OD,400MHz,ppm):9.47(4H,d,J=6.4),8.82(4H,d,J=6.8),7.85(4H,d,J=8.8),7.33(4H,d,J =9.2),4.30(4H,t,J=4.4),3.93(4H,t,J=4.4),3.75(4H,t,J=4.0),3.51-3.69(16H,m),1.20(6H,t, J=7.2).δC(CD3OD,100MHz,ppm):163.22,151.33,146.86,137.00,128.27,126.92,122.80,119.61 ,117.48,71.85,71.65,70.95,70.64,69.55,67.61,15.48.δF(CD3OD,376MHz,ppm):-80.41.Elemental analysis:C 42 H 50 F 12 N4O 16 Calculated value of S4 (1223.10): C, 41.24; H, 4.12; N, 4.58; S, 10.48%. Measured values: C, 41.50; H, 4.21; N, 4.65; S, 10.22%.

[0230] Example 2 Dicationic stilbazolium salts (see structure in Figure 1B) have a DC conductivity of σ dc about 10 -4.5 S cm -1 and their glass transition T g On the other hand, the activation of the σ dc about 10 -2.5 S cm -1 A maximum of N was observed for the asymmetric viologen bistriflimide salts (see FIG. 1C), which is associated with the formation of a liquid crystal smectic T phase and correlates with short-range motion around the rod-like aromatic units. +The location of the site (close to) and its ability to form π-π aggregates could be favorable for ionic conductivity. These results prompted the investigation of novel triflimido viologens with extended core structures, and the conductive properties of novel viologens 1 to 3 prepared via the Zinke reaction were investigated (see Figure 1D).

[0231] Viologens and their numerous derivatives are sought after as functional materials in electrochromic devices, diodes and transistors, memory devices, molecular machines, and dye-sensitized solar cells. The reason for introducing the oxyethylene end is twofold. First, the aim was to counter (at least partially) the rigidity of the four-ring phenyl core, which can increase viscosity. In addition, the presence of polar chains helps to delocalize the triflimide anion, avoiding complexation reactions that can ultimately inhibit ion mobility.

[0232] 4-Oligoethyleneoxyphenylanilines were prepared according to a modified literature procedure. The synthesis of bis-(4-oligoethyleneoxyphenyl)-4,4'-bipyridinium dichlorides (P1 to P3) bearing different ethyleneoxy groups is summarized in Scheme 1. The method involved (i) an aromatic nucleophilic substitution reaction between 1-chloro-2,4-dinitrobenzene and 4,4'-bipyridine in acetonitrile under reflux to obtain the so-called Zinke salt (steps 1 to 2); and (ii) a subsequent anionic ring-opening and ring-closing reaction (ANROC) with the corresponding 4-oligoethyleneoxyphenylaniline at room temperature in N,N-dimethylacetamide (DMAc) (steps 3 to 4). Finally, P1 to P3 were converted to the salts of interest 1 to 3 by metathesis with lithium triflimide in methanol (step 5). The prepared salts were in the form of brown powders, respectively. The chemical structures of intermediates and final products were determined by Fourier transform infrared (FT-IR) spectroscopy in CD3OD, 1 H, 13 C, and 19The purity was confirmed by F nuclear magnetic resonance (NMR) and their purification was determined by elemental analysis. These are believed to be the first examples of ionic liquids prepared via the Zinke reaction.

[0233] The thermal properties and phase behavior of the new salts were determined by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and polarized light microscopy (POM). The three salts exhibited thermal stability up to 300 °C (decomposition temperature, T d The bistriflimide ion was thought to provide high thermal stability, but the high T d The values ​​confirm that the presence of flexible oxyethylene groups does not have a destabilizing effect on the salt.

[0234] [Table 1]

[0235] Figure 2 shows the temperature dependence of the -1Figure 7 shows DSC thermograms of the three salts corresponding to their first heating scans obtained at a rate of 1000 s. While 1 and 2 show first order endotherms associated with the crystal-to-crystal (2) and melting (1 and 2) processes, 3 shows only a glass transition at low temperature (Tg=-6°C). According to these results, both 1 and 2 behave as ionic liquids that melt on heating (the stretching of the oxyethylene ends lowers the melting point). The absence of a first order transition in the corresponding thermograms indicates that 3 behaves similarly to an amorphous salt due to the inhibition of crystallization in the sufficiently long ethyleneoxy chains of n=3. Notable is the absence of further visible thermal events in the subsequent heating and cooling scans of 1 and 2, indicating that crystallization in these samples must be a slow process. See Figures 7A to 7C. The absence of liquid crystalline behavior contrasts with the formation of smectic phases with similar alkoxy-terminated (n≧6) viologens previously observed in this study. Terminal chains of comparable length (see Figure 1E) were expected to promote microphase separation and smectic behavior in 1 to 3, but the formation of stronger interactions through the ethyleneoxy groups may limit the local mobility required to obtain liquid crystallinity. The effect of terminal chain length on nanophase separation between polar chains and the aromatic core of analogous viologens is the subject of further ongoing studies.

[0236] The conductivity response of the viologens is illustrated in Figure 3, which shows their dielectric loss factors ε'' obtained as a function of temperature and frequency and measured in an isothermal process upon heating from room temperature. For further details see the Supplementary Information. These values ​​are significantly higher for the organic media, which is due to the high polarity of the ionic liquids and salts. All log-log ε'' plots show a linear drop (with a slope of about -1) representing an increase in direct current (DC) conductivity at sufficiently low frequencies. Although some peaks are observed for 2 and 3 in Figures 3B and 3C, respectively, the DC component makes any potential dielectric relaxation insubstantial. For these ionic liquids, the isotherms shift with temperature, indicating a thermal activation effect that will be discussed later. Salt 3, on the other hand, shows the highest ε'' value among the three salts. See Figure 3C. The onset of DC conductivity is confirmed by the formation of a plateau in the log-log plot of σ' versus f in Figure 4, which has a similar temperature dependence as the corresponding dielectric loss modulus shown in Figure 3. The DC conductivity values ​​σ dc can be estimated by extrapolating the range where σ' is constant at each temperature to f → 0, and the resulting Arrhenius plot is shown in Figure 5. From the Arrhenius plot, the activation energy E a is the equation;σ dc =σ0exp(E a / RT), where R is the gas constant 8.31 J mol -1 ·K -1 where T is absolute temperature and σ is the pre-exponential term.

[0237] The Cole-Cole plot of 3 is shown in FIG. 8. The AC oscillation voltage was 0.5 V. The results suggest that longer ethyleneoxy end chains increase the conductivity in the salt. Indeed, 3 shows excellent σ 2 , comparable to standard electrolytes used in fuel cells and batteries. dc Value(10 -3.5 S cm -1 From 10 -1.5 S cm -1This material is one of the few examples of organic salts that exhibit such high conductivity under anhydrous conditions and at mild temperatures, even close to room temperature. The activation energy inferred from the Arrhenius plot of the sample is E for 1, a =95.9 kJ mol -1 , 2 for E a =84.5 kJ mol -1 , and E for 3 a =79.4 kJ mol -1 These values ​​are rather high for local activation processes and are in good agreement with the occurrence of so-called β-relaxation involving the rotation of rod-like molecules (elongated viologen moieties) around their long axes within the crystal lattice. It is thought that in the case of short -(CH2CH2O)- terminal chains, the conduction process is dominated (and partly hindered) by the motions around the bulky 4-phenyl core. Alternatively, in salt 3, the plasticizing effect of the longer terminal chains leads to a temperature rise above its low glass transition temperature (T g -6°C (see Figure 2), forming a rubbery phase with a large free volume that facilitates ionic movement (high σ dc values ​​and slightly lower activation energies).

[0238] Novel viologens using the Zinke reaction have been prepared, leading to ionic liquids and salts with strong dielectric responses due to the presence of both flexible oxyethylene groups and triflimide ions. Sufficiently long terminal chains promote very high ionic conductivity at room temperature, comparable to commercially used standard electrolytes, highlighting their potential applications in energy devices, e.g., fuel cells, batteries, supercapacitors, or solar cells. The results of this work open a new field for designing ionic liquids with tailored electrostatic interactions and nanostructures by extending the central rigid core, exchanging it with another cation, or modifying the length of the oxyethylene ends.

Claims

1. An ionic liquid electrolyte comprising a viologen salt of formula (I). 【Chemistry 1】 [In the formula, R １ and R ２ are each independently 【Chemistry 2】 where n is 3-10; m and p each independently represent 1 to 3; R ａ When present, each independently represents C １－４ Alkyl, C １－２ Haloalkyl, -OC １－４ Alkyl, -OC １－２ Haloalkyl, halogen, -NO ２ , -CN, or -(OCH ２ CH ２ ) １－３ OCH ２ CH ３ and R ｂ When present, each independently represents C １－４ Alkyl, C １－２ Haloalkyl, -OC １－４ Alkyl, -OC １－２ Haloalkyl, halogen, -NO ２ , -CN, or -(OCH ２ CH ２ ) １－３ OCH ２ CH ３ and 【Chemistry 3】 are respectively: 【Chemistry 4】 (Wherein, R' is -(OCH ２ CH ２ ) １－１０ OCH ２ CH ３ (It is) is]

2. 2. The ionic liquid electrolyte of claim 1 , wherein m is 1.

3. 2. The ionic liquid electrolyte of claim 1 , wherein p is 1.

4. 2. The ionic liquid electrolyte of claim 1 , wherein m is 2.

5. 2. The ionic liquid electrolyte of claim 1 , wherein p is 2.

6. 2. The ionic liquid electrolyte of claim 1 , wherein the viologen salt of formula (I) is a symmetric viologen salt. 【Request 7】 【Chemical 5】 are respectively, 【Chemistry 6】 The ionic liquid electrolyte of claim 1 .

8. The viologen salt of formula (I) is represented by the formula (I-a): 【Chemistry 7】 2. The ionic liquid electrolyte of claim 1, which is a viologen salt of

9. The viologen salt of formula (I) is represented by formula (I-b): 【Chemistry 8】 2. The ionic liquid electrolyte of claim 1, which is a viologen salt of

10. The viologen salt of formula (I) 【Chemistry 9】 The ionic liquid electrolyte of claim 1 .

11. 2. An all-solid-state battery, a supercapacitor, a solar cell, or a perovskite photovoltaic cell comprising the ionic liquid electrolyte of claim 1.

12. The conductivity of the viologen salt of formula (I) is 0.1 S cm －１ The ionic liquid electrolyte of claim 1 .

13. Cathode; anode A separator; and Ionic Liquid Electrolytes An all-solid-state battery comprising:

1. An all-solid-state battery, wherein the ionic liquid electrolyte comprises a viologen salt of formula (I). 【Chemistry 10】 [In the formula, R １ and R ２ are each independently 【Chemistry 11】 where n is 3-10; m and p each independently represent 1 to 3; R ａ When present, each independently represents C １－４ Alkyl, C １－２ Haloalkyl, -OC １－４ Alkyl, -OC １－２ Haloalkyl, halogen, -NO ２ , -CN, or -(OCH ２ CH ２ ) １－３ OCH ２ CH ３ and R ｂ When present, each independently represents C １－４ Alkyl, C １－２ Haloalkyl, -OC １－４ Alkyl, -OC １－２ Haloalkyl, halogen, -NO ２ , -CN, or -(OCH ２ CH ２ ) １－３ OCH ２ CH ３ and 【Chemistry 12】 are respectively: 【Chemistry 13】 (Wherein, R' is -(OCH ２ CH ２ ) １－１０ OCH ２ CH ３ (It is) is]

14. Cathode; anode; A separator; and Ionic Liquid Electrolytes A supercapacitor comprising: A supercapacitor, wherein the ionic liquid electrolyte comprises a viologen salt of formula (I). 【Chemistry 14】 [In the formula, R １ and R ２ are each independently 【Chemistry 15】 where n is 3-10; m and p each independently represent 1 to 3; R ａ When present, each independently represents C １－４ Alkyl, C １－２ Haloalkyl, -OC １－４ Alkyl, -OC １－２ Haloalkyl, halogen, -NO ２ , -CN, or -(OCH ２ CH ２ ) １－３ OCH ２ CH ３ and R ｂ When present, each independently represents C １－４ Alkyl, C １－２ Haloalkyl, -OC １－４ Alkyl, -OC １－２ Haloalkyl, halogen, -NO ２ , -CN, or -(OCH ２ CH ２ ) １－３ OCH ２ CH ３ and 【Chemistry 16】 are respectively: 【Chemistry 17】 (Wherein, R' is -(OCH ２ CH ２ ) １－１０ OCH ２ CH ３ (It is) is]

15. An n-type semiconductor layer; A p-type semiconductor layer; and Ionic Liquid Electrolytes A solar cell comprising: A solar cell, wherein the ionic liquid electrolyte comprises a viologen salt of formula (I). 【Chemistry 18】 [In the formula, R １ and R ２ are each independently 【Chemistry 19】 where n is 3-10; m and p each independently represent 1 to 3; R ａ When present, each independently represents C １－４ Alkyl, C １－２ Haloalkyl, -OC １－４ Alkyl, -OC １－２ Haloalkyl, halogen, -NO ２ , -CN, or -(OCH ２ CH ２ ) １－３ OCH ２ CH ３ and R ｂ When present, each independently represents C １－４ Alkyl, C １－２ Haloalkyl, -OC １－４ Alkyl, -OC １－２ Haloalkyl, halogen, -NO ２ , -CN, or -(OCH ２ CH ２ ) １－３ OCH ２ CH ３ and 【Chemistry 20】 are respectively: 【Chemistry 21】 (Wherein, R' is -(OCH ２ CH ２ ) １－１０ OCH ２ CH ３ (It is) is]

16. An n-type semiconductor layer; Electron transport layer (ETL); A p-type semiconductor layer; and Ionic Liquid Electrolytes A perovskite photovoltaic cell comprising:

1. A perovskite photovoltaic cell, wherein the ionic liquid electrolyte comprises a viologen salt of formula (I). 【Chemical 22】 [In the formula, R １ and R ２ are each independently 【Chemistry 23】 (wherein n is 3-10). and m and p each independently represent 1 to 3; R ａ When present, each independently represents C １－４ Alkyl, C １－２ Haloalkyl, -OC １－４ Alkyl, -OC １－２ Haloalkyl, halogen, -NO ２ , -CN, or -(OCH ２ CH ２ ) １－３ OCH ２ CH ３ and R ｂ When present, each independently represents C １－４ Alkyl, C １－２ Haloalkyl, -OC １－４ Alkyl, -OC １－２ Haloalkyl, halogen, -NO ２ , -CN, or -(OCH ２ CH ２ ) １－３ OCH ２ CH ３ and 【Chemistry 24】 are respectively: 【Chemistry 25】 (Wherein, R' is -(OCH ２ CH ２ ) １－１０ OCH ２ CH ３ (It is) is]

17. 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell of any one of claims 13 to 16, wherein m is 1.

18. 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell of any one of claims 13 to 16, wherein p is 1.

19. 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell of any one of claims 13 to 16, wherein m is 2.

20. 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell of any one of claims 13 to 16, wherein p is 2.

21. 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell of any one of claims 13 to 16, wherein the viologen salt is a symmetric viologen salt.

22.

26. are respectively, 【Chemical 27】 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell according to any one of claims 13 to 16, wherein

23. The viologen salt of formula (I) is represented by formula (I-a): 【Chemistry 28】 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell of claim 13, wherein the viologen salt is

24. The viologen salt of formula (I) is represented by formula (I-b): 【Chemical 29】 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell of claim 13, wherein the viologen salt is

25. The conductivity of the viologen salt of formula (I) is 0.1 S cm －１ 17. The all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell of claim 13, wherein the capacitance C of the all-solid-state battery, supercapacitor, solar cell, or perovskite photovoltaic cell is greater than or equal to 1.

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