Non-porous electrolyte composites

Abstract

Described herein are non-porous electrolyte composites comprising a plurality of charge-transfer crystals comprising an electron accepting molecule and an electron donating molecule. The charge-transfer crystals are dispersed in a matrix comprising an ionic species and a polymer. The ionic species may be a cation, anion, or a polyanion. The polymer may be a homopolymer or a copolymer. The ionic species and the polymer may be non-covalently or covalently bonded. Also described herein is the implementation of the electrolyte composites into an electrochemical cell.

Description

ND 24-015 NON-POROUS ELECTROLYTE COMPOSITES PRIORITY STATEMENT

[0001] This application claims priority to U.S. Provisional Patent Application No.63 / 660,381, filed on June 14, 2024, and U.S. Provisional Patent Application No. 63 / 602,486, filed on November 24, 2023, each of which are incorporated by reference herein in its entirety. TECHNICAL FIELD

[0002] The present disclosure describes non-porous electrolyte composites capable of facilitating the transport of ions and / or electrons. Also described herein is the integration of the electrolyte composites into an electrochemical cell. INTRODUCTION

[0003] Lithium-ion batteries are widely used in various applications. However, the safety risks due to combustible organic liquid electrolytes have led to significant interest in solid-state electrolytes. Even though inorganic solid electrolytes can have comparable or even higher conductivity than liquid electrolytes, their low mechanical flexibility presents a challenge for commercialization. Crystalline inorganic solid electrolytes can also be difficult to densify, with voids in the electrolyte contributing to lithium dendrite growth in lithium metal batteries. Despite the lower thermal stability, solid organic electrolytes may provide greater durability to withstand volume changes during cycling. Solid-state polymer electrolytes such as those based on poly(ethylene oxide) have been a focus of much attention, as the polar polymers can bind with Li+, enable the lithium salt dissociation, and facilitate the transport of Li+through the amorphous matrix via polymer segmental motion. However, the conductivity of these polar polymer electrolytes is typically low at room temperature, which has led to the exploration of compounds with lower glass-transition temperatures (Tg). The operating temperature of batteries with solid polymer electrolytes is usually elevated to improve conductivity. Efforts to decouple ion conduction from polymer segmental motion have experienced little success and failed to achieve ionic conductivity at the levels necessary for commercialization.

[0004] Thus, there is a need for non-porous solid electrolyte composites capable of facilitating the transport of ions and electrons.ND 24-015 SUMMARY

[0005] The present application discloses electrolyte composites. Described herein are electrolyte composites comprising a plurality of charge-transfer complex crystals dispersed within a matrix comprising an ionic species and a polymer, wherein the charge-transfer complex crystals comprise an organic electron accepting molecule and an organic electron donating molecule. In some embodiments, the composite is non-porous and solvent-free. In some embodiments, the matrix is non-crystalline and non-glassy. In some embodiments, the composite comprises:10– 50% by mass of charge-transfer complex crystals; and 50–90% by mass of the matrix. In some embodiment, the organic electron accepting molecule is selected from a group consisting of tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), and benzoquinone (BQ). In some embodiments, the organic electron donating molecule is selected from a group consisting of hydroquinone (HQ), phenoxazine (PX), thianthrene (TH), pyrene (PY), tetramethyltetraselenafulvalene (TMTSeF), tetrathiafulvalene (TFF), hexamethylenetetraselenafulvalene (HMTTF), hexamethylenetetraselenafulvalene (HMTSF), and bis(ethylenedithio)tetrathiafulvalene (BEDT-TFF). In some embodiments, a charge-transfer crystal in the plurality of charge-transfer complex crystals has an electronic conductivity of at least 10−6S / cm prior to being used in the electrolyte composite. In some embodiments, the charge- transfer complex crystals have a neutral charge-transfer value or non-integer charge-transfer value. In some embodiments, the neutral charge-transfer value of zero. In some embodiments, the non-integer charge-transfer value is between 0 and 1.

[0006] In some embodiments, the ionic species comprises a cation selected from a group consisting of lithium, sodium, potassium, calcium, magnesium, zinc, and aluminum. In some embodiments, the ion species further comprises an anion. In some embodiments, the anion comprises a sulfonate, a bis(sulfonyl)imide, derivatives thereof, and salts thereof. In some embodiments, the anion is selected from a group consisting of bis(pentafluoroethanesulfonyl)imide (BETI), bis(trifluoromethanesulfonyl)imide (TFSI), bis(fluorosulfonyl)imide (FSI), trifluoromethanesulfonate (TfO), and trifluoromethanesulfonate (TF). In some embodiments, the anion comprises a polyatomic anion. In some embodiments, the polyatomic anion is selected from a group consisting of ClO4−, BF4−, and PF6−. In some embodiments, the ionic species further comprises a polyanion. In some embodiments, the polyanion comprises a sulfonate, a bis(sulfonyl)imide, derivatives thereof, and salts thereof. In some embodiments, the polyanion comprises (4-styrenesulfonyl)(trifluoromethanesulfonyl)imide, derivatives thereof, and salts thereof. In some embodiments, the polyanion is selected from a group consisting of poly[(4-styrenesulfonyl)(trifluoromethanesulfonyl)imide] (PSTFSI), poly[3-ND 24-015 [(methacrylate propylsulfonyl)(trifluoromethanesulfonyl)imide] (PAPTFSI), and poly[((6-(2,5- dichlorophenoxy)hexyl)sulfonyl)-((trifluoromethyl)sulfonyl)amide] (PPC6TFSI).

[0007] In some embodiments, the polymer is linear, branched, cross-linked, or a combination thereof. In some embodiments, the polymer comprises at least one polar polymer. In some embodiments, the polymer is a homopolymer comprising a polyether, a polyester, a polyacrylate, a polycarbonate, a polyketone, a polyurea, a poly(ionic liquid), a polythioether, a polythioester, a polythiocarbonate, a polythiourea, or a derivative thereof. In some embodiments, wherein the polymer is a homopolymer comprising a polyethylene oxide, poly[poly(ethylene glycol) methyl ether acrylate] (PEGMA), or derivatives thereof; and salts thereof. In some embodiments, the polymer is a copolymer comprising one or more polar polymers. In some embodiments, the one or more polar polymers comprise a polyether, a polyester, a polyacrylate, a polycarbonate, a polyketone, a polyurea, a poly(ionic liquid), a polythioether, a polythioester, a polythiocarbonate, a polythiourea, derivatives thereof, or combinations thereof. In some embodiments, the one or more polar polymers are selected from a group consisting of poly[poly(ethylene glycol) methyl ether acrylate] (PEGMA), a poly[poly(propylene glycol) methyl ether acrylate], a poly(ethylene oxide) (PEO), a poly[4-styrenesulfonyl(trifluorosulfonylimide)] (PS), a poly[3- ((trifluoromethane)sulfonamidosulfonyl)propyl methacrylate], a poly(ε-caprolactone) (PCL), a poly(trimethylene carbonate) (PTMC), a poly(pentyl malonate), derivatives thereof, and combinations thereof. In some embodiments, the copolymer further comprises one or more non- polar polymers. In some embodiments, the one or more non-polar polymers comprises a polyolefin, a fluoropolymer, an aromatic polymer, or derivatives thereof. In some embodiments, the one or more non-polar polymers is selected from a group consisting of a polyethylene, a polyvinylidene difluoride, or a polystyrene. In some embodiments, the polymer is a copolymer selected from the group consisting of poly(ε-caprolactone)-poly(trimethylene carbonate) (PCL- PTMC), poly(ethylene oxide)-polystyrene (PEO-PS), derivatives thereof, and salts thereof.

[0008] In some embodiments, the matrix is non-covalently bonded. In some embodiments, the matrix selected from the group consisting of PEO-TFSI, PEO-LiBETI, PCL-PTMC-LiTFSI, PEO-LiPPC6TFSI, PEO-Mg(TFSI)2, PEO-NaClO4, and PEO-KBF4. In some embodiments, the matrix is covalently associated. In some embodiments, the matrix is selected from a group consisting of poly[poly(ethylene glycol) methyl ether acrylate]-poly[(4- styrenesulfonyl)(trifluoromethanesulfonyl)imide] lithium salt (PEGMA-LiPSTFSI).

[0009] In some embodiments, the electrolyte composites has an ionic conductivity of at least 10−5S / cm. In some embodiments, the electrolyte composites has an electronic conductivity of at least 10−5S / cm. In some embodiments, the electrolyte composites has an electronic conductivityND 24-015 of at most 10−5S / cm. In some embodiments, the electrolyte composite has an ionic conductivity of at least 125% greater than the ionic conductivity of the matrix.

[0010] In some embodiments, the electrolyte composite further comprises a dopant. In some embodiments, the dopant comprises inorganic particles, fibers, a scaffold, or plasticizer, or a combination thereof.

[0011] Also described herein is an electrochemical cell comprising a negative electrode; a positive electrode; and an electrolyte composite described herein positioned between the negative electrode and the positive electrode. In some embodiments, the electrochemical cell further comprises an electronically insulating material. In some embodiments, the electronically insulating material is positioned between the positive electrode and the electrolyte composite, between the negative electrode and the electrolyte composite, or between both the positive and negative electrodes and the electrolyte composite. In some embodiments, the electronically insulating material between the positive electrode and the electrolyte composite comprises the same materials as the electronically insulating material between the negative electrode and the electrolyte composite. In some embodiments, the electronically insulating material comprises an ionically conductive species, a cross-linked polymer, or a plasticizer. In some embodiments, the electronically insulating material further comprises a porous support.

[0012] Before any embodiments of the disclosure are explained in detail, it is to be understood that the disclosure is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the following drawings. The disclosure is capable of other embodiments and of being practiced or of being carried out in various ways. DESCRIPTION OF DRAWINGS

[0013] FIG.1A–B shows a schematic illustration of a composite electrolyte comprising charge- transfer crystals dispersed in a matrix. FIG.1A shows the matrix (left) containing polar polymer chains with mobile cations and anions. FIG.2A shows the matrix (left) containing polar polymer chains containing substituents bearing a negative charge and mobile cations.

[0014] FIG 2 shows a photograph of a free-standing, solid-state, non-porous, composite electrolyte film of composition PEO-LiTFSI-[TTF-TCNQ] at a ratio of 39-25-36 with thickness of about 100 microns held by tweezers.

[0015] FIG.3 shows the molecular structure of PEGMA-LiPSTFSI, a random graft copolymer with tethered ionic groups.ND 24-015

[0016] FIG.4 shows equivalent circuit models that fit collected AC impedance data in mixed conduction cases where the ionic conductivity exceeds the electronic conductivity by less than 50 times.

[0017] FIG.5 shows equivalent circuit models that fit collected AC impedance data in mixed conduction cases where the ionic conductivity exceeds the electronic conductivity by more than 50 times.

[0018] FIG.6 shows a graph of ionic conductivity as a function of temperature for PEO-LiTFSI in the presence and absence of varying amounts of [TTF-TCNQ]. The composite exhibits conductivity enhancement both when the matrix is semicrystalline (< 0 °C) and when it is melted (> 0 °C).

[0019] FIG.7 shows a graph of ionic conductivity as a function of temperature for PEO-LiBETI in the presence and absence of [TTF-TCNQ].

[0020] FIG.8 shows a graph of ionic conductivity as a function of temperature for PCL-PTMC- LiTFSI in the presence and absence of [TTF-TCNQ].

[0021] FIG. 9 shows a graph of ionic conductivity as a function of temperature for PEGMA- LiPSTFSI in the presence and absence of [TTF-TCNQ].

[0022] FIG. 10 shows a graph of ionic conductivity as a function of temperature for PEO- Mg(TFSI)2in the presence and absence of [TTF-TCNQ].

[0023] FIG. 11 shows a graph of ionic conductivity as a function of temperature for PEO- NaClO4in the presence and absence of [TTF-TCNQ].

[0024] FIG.12 shows a graph of ionic conductivity as a function of temperature for PEO-KBF4in the presence and absence of [TTF-TCNQ].

[0025] FIG.13 shows a graph of ionic conductivity as a function of temperature for PEO-LiTFSI in the presence and absence of [TMTSeF-TCNQ].

[0026] FIG. 14 shows a graph of ionic conductivity as a function of temperature for PEO- LiPPC6TFSI in the presence and absence of [TTF-TCNQ].

[0027] FIG.15 is a differential scanning calorimetry (DSC) thermogram showing the heating and cooling of PEO-LiTFSI-[TTF-TCNQ] at a ratio of 39-25-36.

[0028] FIG.16 shows ionic conductivity as a function of temperature normalized by the glass transition temperature (Tg / T) for PEO-LiTFSI-[TTF-TCNQ] at a ratio of 39-25-36.

[0029] FIG. 17 shows a graph of the experimentally determined ionic conductivity of PEO- LiTFSI-[TTF-TCNQ] at a ratio of 39-25-36 as a function of temperature fit to the equation containing both Arrhenius and Vogel-Fulcher-Tammann temperature-dependent terms.ND 24-015

[0030] FIG.18 is a scanning electron micrograph (SEM) of the [TTF-TCNQ] charge-transfer crystals.

[0031] FIG.19 is a scanning electron micrograph (SEM) of PEO-LiTFSI-[TTF-TCNQ] at a ratio of 39-25-36. The polymer electrolyte is visible as a smooth material that coats and fills the voids between the CT complex particles.

[0032] FIG.20 is a scanning electron micrograph (SEM) of PEO-LiTFSI-[TTF-TCNQ] at a ratio of 39-25-36. The area in the white box is an area where higher beam energy was applied, resulting in the polymer electrolyte phase being etched and shows the arrangement of charge- transfer crystals below the surface of the electrolyte composite.

[0033] FIG. 21 is a graph of X-ray diffraction (XRD) data for PEO-LiTFSI-[TTF-TCNQ] at a ratio of 39-25-36 compared to the matrix (PEO-LiTFSI) and pure CT complex [TTF-TCNQ].

[0034] FIG.22 shows a diagram of an electrochemical cell including at least one electrode and an electrolyte composite comprising a CT complex and a matrix. The electrochemical cell may include an electronically insulating material between one or more electrode(s) and the electrolyte composite.

[0035] FIG. 23 shows a diagram of an electrochemical cell including an anode, electrolyte composite, and a cathode. Also shown is a crosslinker protective layer between the cathode and the electrolyte composite and the anode and the electrolyte composite.

[0036] FIG.24 shows the real portion of the complex conductivity (conductivity’) as a function of frequency at room temperature for electrochemical cells with symmetric stainless steel electrodes separated by PEO-LiTFSI-[TTF-TCNQ] at a ratio of 39-25-36 (denoted as CTPE in the figure legend) and separated by PEO-LiTFSI-[TTF-TCNQ] at a ratio of 39-25-36 and an electronically insulating crosslinked polymer layer comprising poly(polyethylene glycol diacryate), LiTFSI, succinonitrile, and fluoroethylene carbonate separating the electrolyte composite from the stainless steel electrodes (denoted as CPL / CTPE / CPL in the figure legend).

[0037] FIG.25 shows the ionic conductivity as a function of temperature for electrochemical cells with symmetric stainless steel electrodes separated by PEO-LiTFSI-[TTF-TCNQ] at a ratio of 39-25-36 and electronically insulating crosslinked polymer layers between the composite electrolyte and the stainless steel electrodes. The electronically insulating crosslinked polymer layers vary between the freestanding electronically insulating crosslinked polymer layer comprising poly(polyethylene glycol diacryate), LiTFSI, succinonitrile, and fluoroethylene carbonate compared with the cellulose-based layer comprising poly(polyethylene glycol diacryate), LiTFSI, succinonitrile, fluoroethylene carbonate, and a cellulose scaffold.ND 24-015

[0038] FIG. 26 shows the impedance for electrochemical cells with symmetric lithium metal electrodes separated by PEO-LiTFSI-[TTF-TCNQ] at a ratio of 39-25-36 and electronically insulating crosslinked polymer layers between the composite electrolyte and the stainless steel electrodes. The electronically insulating crosslinked polymer layers are both the freestanding electronically insulating crosslinked polymer layer comprising poly(polyethylene glycol diacryate), LiTFSI, succinonitrile, and fluoroethylene carbonate.

[0039] FIG. 27 shows a graph of galvanostatic cycling at room temperature of an electrochemical cell with symmetric lithium metal electrodes separated by PEO-LiTFSI-[TTF- TCNQ] at a ratio of 39-25-36 and an electronically insulating crosslinked polymer layer comprising poly(polyethylene glycol diacryate), LiTFSI, succinonitrile, and fluoroethylene carbonate separating the electrolyte composite from the lithium metal electrodes.

[0040] FIG.28 shows a graph of galvanostatic cycling at room temperature of electrochemical cells with symmetric lithium metal electrodes separated by PEO-LiTFSI-[TTF-TCNQ] at a ratio of 39-25-36 (denoted as CTPE in the figure legend) and separated by PEO-LiTFSI-[TTF-TCNQ] at a ratio of 39-25-36 and an electronically insulating crosslinked polymer layer comprising poly(polyethylene glycol diacryate), LiTFSI, succinonitrile, and fluoroethylene carbonate separating the electrolyte composite from the stainless steel electrodes (denoted as CPL / CTPE / CPL in the figure legend). DETAILED DESCRIPTION

[0041] Before any embodiments of the disclosure are explained in detail, it is to be understood that the disclosure is not limited in its application to the details of construction and the arrangement of components set forth in the following description or illustrated in the following drawings. The disclosure is capable of other embodiments and of being practiced or of being carried out in various way.

[0042] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present document, including definitions, will control. Preferred methods and materials are described below, although methods and materials similar or equivalent to those described herein can be used in practice or testing of the present invention. All publications, patent applications, patents and other references mentioned herein are incorporated by reference in their entirety. The materials, methods, and examples disclosed herein are illustrative only and not intended to be limiting.ND 24-015

[0043] The following explanations of terms are provided to better detail the descriptions of aspects, embodiments and objects that will be set forth in this section. Unless explained or defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. In order to facilitate review of the various embodiments of the disclosure, the following explanations of specific terms are provided:

[0044] The terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that do not preclude the possibility of additional acts or structures. The singular forms “a,” “an” and “the” include plural references unless the context clearly dictates otherwise. The present disclosure also contemplates other embodiments “comprising,” “consisting of” and “consisting essentially of,” the embodiments or elements presented herein, whether explicitly set forth or not.

[0045] The modifier “about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (for example, it includes at least the degree of error associated with the measurement of the particular quantity). The modifier “about” should also be considered as disclosing the range defined by the absolute values of the two endpoints. For example, the expression “from about 2 to about 4” also discloses the range “from 2 to 4.” The term “about” may refer to plus or minus 10% of the indicated number. For example, “about 10%” may indicate a range of 9% to 11%, and “about 1” may mean from 0.9–1.1. Other meanings of “about” may be apparent from the context, such as rounding off, so, for example “about 1” may also mean from 0.5 to 1.4.

[0046] As used herein “or” can mean the conjunctive or disjunctive. For example, two actions separated by an “or” can be performed either simultaneously, sequentially, or separately.

[0047] Definitions of specific functional groups and chemical terms are described in more detail below. For purposes of this disclosure, the chemical elements are identified in accordance with the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75thed., inside cover, and specific functional groups are generally defined as described therein. Additionally, general principles of organic chemistry, as well as specific functional moieties and reactivity, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March March’s Advanced Organic Chemistry, 5thed., John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3rded. Cambridge University Press, Cambridge, 1987; the entire contents of each of which are incorporated herein by reference.ND 24-015

[0048] The term “alkoxy,” as used herein, refers to a group –O–alkyl. Representative examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, 2-propoxy, butoxy and tert-butoxy.

[0049] The term “alkyl,” as used herein, means a straight or branched, saturated hydrocarbon chain. The term “lower alkyl” or “C1-6alkyl” means a straight or branched chain hydrocarbon containing from 1 to 6 carbon atoms. The term “C1-4alkyl” means a straight or branched chain hydrocarbon 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.

[0050] The term “alkenyl,” as used herein, means a straight or branched, hydrocarbon chain containing at least one carbon-carbon double bond.

[0051] 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.

[0052] The term “alkylamino,” as used herein, means at least one alkyl group, as defined herein, is appended to the parent molecular moiety through an amino group, as defined herein.

[0053] The term “amide,” as used herein, means –C(O)NR– or –NRC(O)–, wherein R may be hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, alkenyl, or heteroalkyl.

[0054] 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.

[0055] The term “amino,” as used herein, means –NRxRy, wherein Rxand Rymay be hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, alkenyl, or heteroalkyl. In the case of an aminoalkyl group or any other moiety where amino appends together two other moieties, amino may be – NRx–, wherein Rxmay be hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, alkenyl, or heteroalkyl.

[0056] The term “aryl,” as used herein, refers to a phenyl or a phenyl appended to the parent molecular moiety and fused to a cycloalkane group (e.g., the aryl may be indan-4-yl), fused to a 6-membered arene group (i.e., the aryl is naphthyl), or fused to a non-aromatic heterocycle (e.g., the aryl may be benzo[d][1,3]dioxol-5-yl). The term “phenyl” is used when referring to a substituent and the term 6-membered arene is used when referring to a fused ring. The 6- membered arene is monocyclic (e.g., benzene or benzo). The aryl may be monocyclic (phenyl) or bicyclic (e.g., a 9- to 12-membered fused bicyclic system).

[0057] The term “cyanoalkyl,” as used herein, means at least one –CN group, is appended to the parent molecular moiety through an alkylene group, as defined herein.ND 24-015

[0058] The term “cycloalkoxy,” as used herein, refers to a cycloalkyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom.

[0059] The term “cycloalkyl” or “cycloalkane,” as used herein, refers to a saturated ring system containing all carbon atoms as ring members and zero double bonds. The term “cycloalkyl” is used herein to refer to a cycloalkane when present as a substituent. A cycloalkyl may be a monocyclic cycloalkyl (e.g., cyclopropyl), a fused bicyclic cycloalkyl (e.g., decahydronaphthalenyl), or a bridged cycloalkyl in which two non-adjacent atoms of a ring are linked by an alkylene bridge of 1, 2, 3, or 4 carbon atoms (e.g., bicyclo[2.2.1]heptanyl). 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.

[0060] The term “cycloalkenyl” or “cycloalkene,” as used herein, means a non-aromatic monocyclic or multicyclic ring system containing all carbon atoms as ring members and at least one carbon-carbon double bond and preferably having from 5-10 carbon atoms per ring. The term “cycloalkenyl” is used herein to refer to a cycloalkene when 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 in which two non-adjacent atoms of a ring are linked by an alkylene bridge of 1, 2, 3, or 4 carbon atoms (e.g., bicyclo[2.2.1]heptenyl). Exemplary monocyclic cycloalkenyl rings include cyclopentenyl, cyclohexenyl or cycloheptenyl. Exemplary monocyclic cycloalkenyl rings include cyclopentenyl, cyclohexenyl or cycloheptenyl.

[0061] The term “carbocyclyl” means a “cycloalkyl” or a “cycloalkenyl.” The term “carbocycle” means a “cycloalkane” or a “cycloalkene.” The term “carbocyclyl” refers to a “carbocycle” when present as a substituent.

[0062] The terms “cycloalkylene” and “heterocyclylene” refer to divalent groups derived from the base ring, i.e., cycloalkane, heterocycle. For illustration, an example cycloalkylene may becyclohexene or and a heterocyclylene may . Cycloalkylene and heterocyclyleneinclude agroups such as 1,1-A further example is 1,1- cyclopropylene.

[0063] The term “halogen” or “halo,” as used herein, means Cl, Br, I, or F.

[0064] The term “haloalkyl,” 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 a halogen.

[0065] The term “haloalkoxy,” as used herein, means at least one haloalkyl group, as defined herein, is appended to the parent molecular moiety through an oxygen atom.ND 24-015

[0066] The term “halocycloalkyl,” as used herein, means a cycloalkyl group, as defined herein, in which one or more hydrogen atoms are replaced by a halogen.

[0067] The term “heteroalkyl,” as used herein, means an alkyl group, as defined herein, in which one or more of the carbon atoms has been replaced by a heteroatom selected from S, O, P and N. Representative examples of heteroalkyls include, but are not limited to, alkyl ethers, secondary and tertiary alkyl amines, amides, and alkyl sulfides.

[0068] The term “heteroaryl,” as used herein, refers to an aromatic monocyclic heteroatom- containing ring (monocyclic heteroaryl) or a bicyclic ring system containing at least one monocyclic heteroaromatic ring (bicyclic heteroaryl). The term “heteroaryl” is used herein to refer to a heteroarene when present as a substituent. The monocyclic heteroaryl are five or six membered rings containing 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). The five membered aromatic monocyclic rings have two double bonds, and the six membered aromatic monocyclic rings have three double bonds. The bicyclic heteroaryl is an 8- to 12- membered ring system and includes a fused bicyclic heteroaromatic ring system (i.e., 10π electron system) such as a monocyclic heteroaryl ring fused to a 6-membered arene (e.g., quinolin-4-yl, indol-1-yl), a monocyclic heteroaryl ring fused to a monocyclic heteroarene (e.g., naphthyridinyl), and a phenyl fused to a monocyclic heteroarene (e.g., quinolin-5-yl, indol-4-yl). A bicyclic heteroaryl / heteroarene group includes a 9-membered fused bicyclic heteroaromatic ring system having four double bonds and at least one heteroatom contributing a lone electron pair to a fully aromatic 10π electron system, such as ring systems with a nitrogen atom at the ring junction (e.g., imidazopyridine) or a benzoxadiazolyl. A bicyclic heteroaryl also includes a fused bicyclic ring system composed of one heteroaromatic ring and one non-aromatic ring such as a monocyclic heteroaryl ring fused to a monocyclic carbocyclic ring (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). The bicyclic heteroaryl is attached to the parent molecular moiety at an aromatic ring atom. Other representative examples of heteroaryl include, but are not limited to, 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., benzimidazol-5-yl), 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,ND 24-015 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.

[0069] 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 when present as a substituent. The monocyclic heterocycle is a three-, four-, five-, six-, seven-, or eight-membered ring containing at least one heteroatom independently selected from the group consisting of O, N, and S. The three- or four-membered ring contains zero or one double bond, and one heteroatom selected from the group consisting of O, N, and S. The five-membered ring contains zero or one double bond and one, two or three heteroatoms selected from the group consisting of O, N and S. The six-membered ring contains zero, one or two double bonds and one, two, or three heteroatoms selected from the group consisting of O, N, and S. The seven- and eight-membered rings contains zero, one, two, or three double bonds and one, two, or three heteroatoms selected from the group consisting of O, N, and S. Representative examples of monocyclic heterocyclyls include, but are not limited to, 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, oxepanyl, 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 (thiomorpholine sulfone), thiopyranyl, and trithianyl. The 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 spiro heterocycle group, or a bridged monocyclic heterocycle 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 two, three, or four carbon atoms. The 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, but are not limited to, 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), 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-ND 24-015 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 a bicyclic heterocycle 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 two, three, or four 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). The monocyclic, bicyclic, and tricyclic heterocyclyls are connected to the parent molecular moiety at a non-aromatic ring atom.

[0070] The term “hydroxyl” or “hydroxy,” as used herein, means an –OH group.

[0071] The term “hydroxyalkyl,” as used herein, means at least one –OH group, is appended to the parent molecular moiety through an alkylene group, as defined herein.

[0072] Terms such as “alkyl,” “cycloalkyl,” “alkylene,” etc. may be preceded by a designation indicating the number of atoms present in the group in a particular instance (e.g., “C1-4alkyl,” “C3-6cycloalkyl,” “C1-4alkylene”). These designations are used as generally understood by those skilled in the art. For example, the representation “C” followed by a subscripted number indicates the number of carbon atoms present in the group that follows. Thus, “C3alkyl” is an alkyl group with three carbon atoms (i.e., n-propyl, isopropyl). Where a range is given, as in “C1-4,” the members of the group that follows may have any number of carbon atoms falling within the recited range. A “C1-4alkyl,” for example, is an alkyl group having from 1 to 4 carbon atoms, however arranged (i.e., straight chain or branched).

[0073] The term “substituted” refers to a group that may be further substituted with one or more non-hydrogen substituent groups. Substituent groups 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.

[0074] Generally, the electrolyte composites of the present disclosure comprise a plurality of charge-transfer complex crystals dispersed within a matrix comprising an ionic species and aND 24-015 polymer. The charge transfer complexes crystals comprise an organic electron accepting molecule and an organic electron donating molecule. The electrolyte composite may be ionically conductive, electronically conductive, or a combination of ionically conductive and electronically conductive.

[0075] Various embodiments of the electrolyte composites are disclosed herein. In some embodiments, an electrolyte composite comprises a plurality of charge-transfer complex crystals dispersed within a matrix comprising an ionic species and a polymer, wherein the charge-transfer complex crystals comprise an organic electron accepting molecule and an organic electron donating molecule.

[0076] In some embodiments, the electrolyte composite comprises a plurality of charge- transfer complex crystals dispersed within a matrix comprising a cation, an anion, and a polymer, wherein the charge-transfer complex crystals comprise an organic electron accepting molecule and an organic electron donating molecule.

[0077] In some embodiments, the electrolyte composite comprises a plurality of charge- transfer complex crystals dispersed within a matrix comprising a cation, an anion, and a polar polymer, wherein the charge-transfer complex crystals comprise an organic electron accepting molecule and an organic electron donating molecule.

[0078] In some embodiments, the electrolyte composite comprises a plurality of charge- transfer complex crystals dispersed within a matrix comprising a cation, an anion, and a homopolymer, wherein the charge-transfer complex crystals comprise an organic electron accepting molecule and an organic electron donating molecule.

[0079] In some embodiments, the electrolyte composite comprises a plurality of charge- transfer complex crystals dispersed within a matrix comprising a cation, an anion, and a copolymer, wherein the charge-transfer complex crystals comprise an organic electron accepting molecule and an organic electron donating molecule.

[0080] In some embodiments, the electrolyte composite comprises a plurality of charge- transfer complex crystals dispersed within a matrix comprising a polyanion and a polymer, wherein the charge-transfer complex crystals comprise an organic electron accepting molecule and an organic electron donating molecule.

[0081] In some embodiments, the electrolyte composite comprises a plurality of charge- transfer complex crystals dispersed within a matrix comprising a polyanion and a polar polymer, wherein the charge-transfer complex crystals comprise an organic electron accepting molecule and an organic electron donating molecule.ND 24-015

[0082] In some embodiments, the electrolyte composite comprises a plurality of charge- transfer complex crystals dispersed within a matrix comprising a polyanion and a homopolymer, wherein the charge-transfer complex crystals comprise an organic electron accepting molecule and an organic electron donating molecule.

[0083] In some embodiments, the electrolyte composite comprises a plurality of charge- transfer complex crystals dispersed within a matrix comprising a polyanion and a copolymer, wherein the charge-transfer complex crystals comprise an organic electron accepting molecule and an organic electron donating molecule.

[0084] In some embodiments, the electrolyte composites of the present disclosure may be non-porous, solvent-free, or a combination of non-porous and solvent-free. As used herein “a non-porous electrolyte composite” refers to an electrolyte composite substantially free of voids or pores within the electrolyte composite. The absence of voids or pores may result in more improved mechanical properties and / or more uniform electric field distribution. As used herein, a “solvent-free electrolyte composite” is characterized by the absence of solvent within or surrounding the electrolyte composite. Exemplary solvents that may be absent from the electrolyte composite, include but are not limited to, water, ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), 1,2- dimethyloxyethane (DME), fluoroethylene carbonate (FEC), 1,3-dioxolane (DOL), acetonitrile, N,N-dimethylformamide (DMF), dimethyl sulfoxide, and methanol (MeOH).

[0085] In some embodiments, the electrolyte composites of the present disclosure may be solid. As used herein, a “solid” describes the ability of an electrolyte composite to keep its shape over an indefinitely long period and is distinguished and different from an electrolyte in a liquid phase. The atomic structure of solids can be either crystalline, amorphous, or semi-crystalline. As used herein “amorphous” may be used interchangeable with “non-crystalline” and is characterized by being substantially free of crystalline structures. “Semi-crystalline,” as used herein, describes a material that is partially crystalline and partially amorphous. In some embodiments, the electrolyte composites may be semi-crystalline.

[0086] In some embodiments, the matrix in which a plurality of charge-transfer complex crystals may be dispersed may also be a solid. In some embodiments, the matrix comprising an ionic species and a polymer may be non-crystalline. A “polymer,” as used herein, is typically organic and comprises carbon-based macromolecules, each of which have one or more type of repeating units or monomers. Polymers are light-weight, ductile, usually non-conductive and melt at relatively low temperatures. Polymers may have a glassy state at temperatures below the glass transition temperature (Tg). Glass transition temperature is a function of chain flexibilityND 24-015 and occurs when there is enough vibrational (thermal) energy in the system to create sufficient free-volume to permit sequences of segments of the polymer macromolecule to move together as a unit. However, in the glassy state of a polymer, there is no segmental motion of the polymer. Correspondingly, “non-glassy,” as used herein, is characterized by the ability of a polymer to have some degree of segmental motion while maintaining the shape of a material in which it exists. In other words, non-glassy describes instances where a polymer with some degree of segmental is completely non-glassy and partially non-glassy. In some embodiments, the matrix of the electrolyte composite is non-glassy. In some embodiment, the matrix of the electrolyte composite is partially non-glassy.

[0087] In some embodiments, the electrolyte composite may comprise about 10 % to about 50% by mass of charge-transfer complex crystals. In some embodiments, the electrolyte composite may comprise 10% to 20% by mass, 10% to 25% by mass, 10% to 30% by mass, 10% to 35% by mass, 10% to 40% by mass, 10% to 45% by mass, 10% to 10% by mass, 20% to 25% by mass, 20% to 30% by mass, 20% to 35% by mass, 20% to 40% by mass, 20% to 45% by mass, 20% to 50% by mass, 30% to 45% by mass, 30% to 50% by mass, or 40% to 50% by mass of charge-transfer complex crystals, including all non-integers and ranges in-between. In some embodiments, the electrolyte composite may comprise no greater than 50% by mass, no greater than 45% by mass, no greater than 40% by mass, no greater than 35% by mass, no greater than 30% by mass, no greater than 25% by mass, no greater than 20% by mass, no greater than 15% by mass, or no greater than 10% by mass charge-transfer complex crystals. In some embodiments, the electrolyte composite may comprise no less than 10% by mass, no less than 15% by mass, no less than 20% by mass, no less than 25% by mass, no less than 30% by mass, no less than 35% by mass, no less than 40% by mass, no less than 45% by mass, or no less than 50% by mass charge-transfer complex crystals. In some embodiments, the electrolyte composite may comprise 10%, 12%, 14%, 16%, 18%, 20%, 22%, 24%-, 26%, 28%, 30%, 32%, 34%-, 36%, 38%, 40%, 42%, 44%, 46%-, 48%-, or 50% by mass charge-transfer complex crystals.

[0088] In some embodiments, the electrolyte composite may comprise about 50% to about 90% by mass of the matrix. In some embodiments, the electrolyte composite may comprise 50% to 60% by mass, 50% to 65% by mass, 50% to 70% by mass, 50% to 75% by mass, 50% to 80% by mass, 50% to 85% by mass, 50% to 90% by mass, 60% to 70% by mass, 60% to 75% by mass, 60% to 80% by mass, 60% to 85% by mass, 60% to 90% by mass, 70% to 80% by mass, 70% to 85% by mass, 70% to 90% by mass, or 80% to 90% by mass of the matrix, including all non-integers and ranges in-between. In some embodiments, the electrolyte composite may comprise no greater than 90% by mass, no greater than 85% by mass, no greater than 80% byND 24-015 mass, no greater than 75% by mass, no greater than 70% by mass, no greater than 65% by mass, no greater than 60% by mass, no greater than 55% by mass, or no greater than 50% by mass of the matrix. In some embodiments, the electrolyte composite may comprise no less than 50% by mass, no less than 55% by mass, no less than 60% by mass, no less than 65% by mass, no less than 70% by mass, no less than 75% by mass, no less than 80% by mass, no less than 85% by mass, or no less than 90% by mass of the matrix. In some embodiments, the electrolyte composite may comprise 50%, 52%, 54%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70%, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86%, 88%, or 90% by mass of the matrix.

[0089] In some embodiments, the organic electron accepting molecule is any molecule comprising carbon and having at least one available empty orbital in its electronic structure than can accommodate one or more incoming electron. Organic electron accepting molecules in the charge-transfer complex crystals may include, but are not limited to, tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), and benzoquinone (BQ).

[0090] In some embodiments, the organic electron donating molecule is any molecule comprising carbon and have one or more electrons that may be transferred to a molecule having at least one available empty orbital (e.g., electron accepting molecule). Organic electron donating molecules in the charge-transfer complex crystals may include, but are not limited to, hydroquinone (HQ), phenoxazine (PX), thianthrene (TH), pyrene (PY), and tetrathiafulvalene (TFF), hexamethylenetetraselenafulvalene (HMTTF), hexamethylenetetraselenafulvalene (HMTSF), bis(ethylenedithio)tetrathiafulvalene (BEDT-TFF).

[0091] Any organic electron accepting molecule and organic electron donating molecule may be combined to form charge-transfer complex crystals by any methods known to a person of ordinary skill in the art. A balance between ionic conductivity and electronic conductivity may allow for the movement of ions and electrons for use in electrochemical systems, such as but not limited to, a battery. As used herein, “ionic conductivity” is characterized by the mobility of at least one charged ion in a system. “Electronic conductivity,” as used herein, is characterized by the mobility of free electrons from a first molecule to second molecule and so forth, where the first and second molecule may have the same identity or different. Charge transfer complexes comprising an organic electron accepting molecule and an organic electron donating molecule may have a significant amount of electronic conductivity due to the electron accepting and donating nature of the molecules. Without being bound by theory, the use of polymers and ions may increase the distance between the electron accepting and electron donating of molecules in the charge-transfer complex and reduce the electronic conductivity of the charge-transfer complex. In some embodiments, a charge transfer crystal formed by one organic electronND 24-015 accepting molecule and one organic electron donating molecule has an electronic conductivity of at least 10−6S / cm outside and prior to being added to the electrolyte composite.

[0092] As used herein, “charge-transfer value” refers to the ability of a molecule to transfer electrons. A charge transfer value may be zero, a non-integer value between 0 and 1, or an integer value of 1. When the charge-transfer value of a molecular is zero, electrons of a molecule are not transferred to a different molecule. A charge-transfer value that is a non-integer value between 0 and 1 indicates a percentage of electrons transferred from one molecule to another. A charge-transfer value of 1, indicates that all electrons are transferred from one molecule to another. In some embodiments, the charge-transfer complex crystals as disclosed herein have a neutral charge-transfer value or a non-integer charge-transfer value. In some embodiments, the charge-transfer complex crystals have a neutral value of zero. In some embodiments, the charge-transfer complex crystal have a non-integer charge-transfer crystals have a non-integer charge-transfer value between 0 and 1. In some embodiments, the charge-transfer value of 0.2– 0.8.

[0093] The matrix of the electrolyte composite may comprise an ionic species. In some embodiments, the ionic species is a cation. In some embodiments, the cation may be selected from a group consisting of lithium, sodium, potassium, calcium, magnesium, zinc, and aluminum.

[0094] In some embodiments, the ionic species may further comprise an anion. In some embodiments, the anion may comprise a sulfonate, a bis(sulfonyl)imide, derivatives thereof, and salts thereof. Exemplary anions that may be used in the electrolyte composites disclosed herein include, but are not limited to, N-methanesulfonylvinylsulfonimide (MSVSI), 2-[2-(2-methoxy ethoxy)ethoxy]ethanesulfonyl(trifluoromethanesulfonyl) imide (ETFSI), 1,1,1-trifluoro-N-[2-[2-(2- methoxyethoxy)ethoxy)]ethyl]methanesulfonamide (FEA), bis(pentafluoroethanesulfonyl)imide (BETI), bis(trifluoromethanesulfonyl)imide (TFSI), bis(fluorosulfonyl)imide (FSI), trifluoromethanesulfonate (TfO), and fluorinated aryl sulfonimide-tagged monomers (FAST) (see e.g., Stolberg et a. Lamellar ionenes with highly dissociative, anionic channels provide lower barriers for cation transport. Journal of the American Chemical Society, 2023, 145, 16200–16209, incorporate by reference herein in its entirety). In some embodiments, the anion may be selected from a group consisting of bis(pentafluoroethanesulfonyl)imide (BETI), bis(trifluoromethanesulfonyl)imide (TFSI), bis(fluorosulfonyl)imide (FSI), and trifluoromethanesulfonate (TfO).

[0095] In some embodiments, the anion may comprise a polyatomic anion. As used herein, a “polyatomic anion” is any molecule having two or more atoms covalently bonded. Exemplary polyatomic anions that may be used in the electrolyte composites disclosed herein include, butND 24-015 are not limited to, ClO4−, BF4−, PF6−, SO42−, SO32−, CH3COO−, ClO3−, PO43−, PO33−, NO3−, and NO2−. In some embodiments, the polyatomic anion may be selected from a group consisting of ClO4−, BF4−, and PF6−.

[0096] In some embodiments, the ionic species further comprises a polyanion. As described herein, a “polyanion” is any molecule comprising a polymeric backbone with repeating units of a substituent bearing a negative charge. The term “polyanion” may be used interchangeably with “single-ion conducting polymer” and “ionomer.” In some embodiments, the polymer may be a copolymer. In some embodiments, the substituent bearing the negative charge may exist as a salt with an additional cation. In some instances, the cation of the substituent bearing the negative charge may possess the same or different identity of the cation in the ionically conductive composite electrolyte. In some embodiments, the polyanion comprises a sulfonate, a bis(sulfonyl)imide, derivatives thereof, and salts thereof. Exemplary polyanions that may be used in the electrolyte composites described herein include, but are not limited to, (4- styrenesulfonyl)(trifluoromethanesulfonyl)imide, derivatives thereof, and salts thereof. In some embodiments the polyanion comprises poly[(4-styrenesulfonyl)(trifluoromethanesulfonyl)imide] (PSTFSI), poly[3-[(methacrylate propylsulfonyl)(trifluoromethanesulfonyl)imide] (PAPTFSI), and poly[((6-(2,5-dichlorophenoxy)hexyl)sulfonyl)-((trifluoromethyl)sulfonyl)amide] (PPC6TFSI). Additional polyanions exist and may also be used in the electrolyte composites described herein (see e.g., Lu et al., Eutectiv Impetus for Single-Cation Conduction in Unadorned Sulfonated Ionomers. ACS Energy Letters, 2023, 8, 4923–4931; Van Humbeck et al. Tetraarylborate polymer networks as single-ion conducting solid electrolytes. Chemical Science, 2015, 6, 5499; Weber, R.L. and Mahanthappa, M.K. Thiol-ene synthesis and characterization of lithium bis(malonato)borate single-ion conducting gel polymer electrolytes. Soft Matter, 2017, 13, 7633; Ma et al. Single lithium-ion conducting polymer electrolytes based on a super-delocalized polyanion. Angewandte Chemie International Edition, 2016, 55, 2521–2525; Wang et al. Fast Li+ transport polyurethane-based single-ion conducting polymer electrolyte with sulfonamide side chains in the hard segment for lithium metal batteries. ACS Applied Materials & Interfaces, 2023, 15, 39837–39846, each incorporated by reference in their entirety).

[0097] The matrix of the electrolyte may comprise a polymer. In some embodiments, the polymer may be linear, branched, cross-linked, or a combination thereof. In some embodiments, the polymer may comprise at least one polar polymer. In some embodiments, the polymer may be a homopolymer. In some embodiments, the polymer may be a homopolymer comprising a polyether, a polyester, a polyacrylate, a polycarbonate, a polyketone, a polyurea, a poly(ionic liquid), a polythioether, a polythioester, a polythiocarbonate, a polythiourea, or derivatives thereof.ND 24-015 As used herein “poly(ionic liquid)” refers to ionic polymers which carry an ionic liquid species in each of the repeating units. An “ionic liquid,” as used herein, is a substance composed of only anions and cations (a salt) that is melted (non-crystalline, amorphous) below 100 °C. Either the cationic or the anionic species may be polymerized in a poly(ionic liquid). Exemplary poly(ionic liquids) that may be used in the matrix of the electrolyte composites disclosed herein include, but are not limited to, poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (PDADMATFSI) and poly(1-ethyl-3-vinylimidazolium bis(trifluoromethanesulfonylimide) (PEMIMTFSI). Exemplary polymers that may be used in the matrix of the electrolyte composites disclosed herein include, but are not limited to, poly(ethylene oxide) / poly(ethylene glycol) (PEO / PEG); poly[poly(ethylene glycol) methyl ether acrylate] (PPEGMEA); poly(ε-caprolactone) (PCL); poly(trimethylene carbonate) (PTMC); poly(pentyl malonate) (PPM); poly(acrylonitrile) (PAN); poly(propylene oxide) / poly(propylene glycol) (PPO / PPG); poly(pentanediol adipate); poly(propylene carbonate) (PPC); poly(ethylene carbonate) (PEC); poly(tetrahydrofuran) (PTHF); poly(dodecamethylene carbonate); salts thereof; and derivatives thereof. In some embodiments, the polymer may be a homopolymer comprising polyethylene oxide or derivatives thereof.

[0098] In some embodiments, the polymer may be a copolymer. In some embodiments, the copolymer may comprise one or more polar polymers. In some embodiments, the one or more polar polymers of the copolymer may comprise a polyether, a polyester, a polyacrylate, a polycarbonate, a polyketone, a polyurea, a poly(ionic liquid), a polythioether, a polythioester, a polythiocarbonate, a polythiourea, derivatives thereof, or combinations thereof. In some embodiments, the one or more polar polymers are selected from a group consisting of poly[poly(ethylene glycol) methyl ether acrylate] (PPEGMEA), a poly[poly(propylene glycol) methyl ether acrylate], a poly(ethylene oxide) (PEO), a poly[4- styrenesulfonyl(trifluorosulfonylimide)] (PSTFSI), a poly[3- ((trifluoromethane)sulfonamidosulfonyl)propyl methacrylate], a poly(ε-caprolactone) (PCL), a poly(trimethylene carbonate) (PTMC), a poly(pentyl malonate), derivatives thereof, and combinations thereof.

[0099] In some embodiment, the copolymer may comprise one or more non-polar polymers. In some embodiments, the one or more non-polar polymers may comprise a polyolefin, a fluoropolymer, an aromatic polymer, or combinations thereof. In some embodiments, the one or more non-polar polymers may be selected from a group consisting of a polyethylene, a polyvinylidene difluoride, or a polystyrene.

[0100] In some embodiments, the copolymer may comprise two differ polar polymers. In some embodiments, the copolymer may comprise at least one polar polymer and a non-polar polymer.ND 24-015 In some embodiments, the copolymer may comprise a polar polymer and a non-polar polymer. Exemplary copolymers that may be used in the electrolyte composite disclosed herein include, but are not limited to, poly(ethylene oxide)-polystyrene (PEO-PS); poly(ε-caprolactone)- poly(trimethylene carbonate) (PCL-PTMC); poly(ethylene glycol)-poly(propylene glycol) (PEG- PPG); poly[poly(ethylene glycol) methyl ether acrylate]-polystyrene (PPEGMEA-PS); poly(1,3- dioxolane)-poly(1,3,5-trioxane) (PDOL-PTXE); poly(ethylene glycol) diglycidal ether- (propylene glycol)-poly(ethylene glycol) diamine (PEGDGE-PEA); poly(ethylene oxide)-poly(ethylene carbonate) (PEO-PEC); poly(ethylene glycol) diacrylate- poly(1-ethyl-3-vinylimidazolium bis(trifluoromethanesulfonylimide) (PEGDA-PEMIMTFSI); poly(siloxane)-poly(ethylene glycol) (PSi-PEG); hydrogenated nitrile butadiene rubber (HNBR); salts thereof; and derivatives thereof. In some embodiments, the copolymer may be selected from a group consisting of poly[poly(ethylene glycol) methyl ether acrylate], a poly[4-styrenesulfonyl(trifluorosulfonylimide)], a poly[3-((trifluoromethane)sulfonamidosulfonyl)propyl methacrylate], and a poly[poly(propylene glycol) methyl ether acrylate], and derivatives thereof.

[0101] The matrix may be any combination of the components described herein. Exemplary matrices that may be used in the electrolyte composites disclosed herein include, but are not limited to, poly[(4-styrenesulfonyl)(trifluoromethanesulfonyl)imide] lithium salt (LiPSTFSI); poly[3- [(methacrylate propylsulfonyl)(trifluoromethanesulfonyl)imide] sodium salt (NaMAPTFSI); poly[3- ((trifluoromethane)sulfonamidosulfonyl)propyl acrylate lithium salt (LiPAPTFSI); poly(styrene sulfonate) sodium salt (NaPSS); poly[(paraphenylene- oxyhexylsulfonyl)(trifluoromethanesulfonyl)imide] lithium salt (LiPPC6TFSI); poly[(4- styrenesulfonyl)(trifluoromethyl(S-trifluoromethyl-sulfonylimino)sulfonyl)imide] lithium salt (LiPSsTFSI); poly(butyl(2-((2-((1,1,1,3,3,3-hexafluoropropan-2-yl (2-(2-(2- methoxyethoxy)ethoxy) ethyl) boryl)oxy)ethyl methacrylate)) lithium salt (LiBB(OGlyO6FiP)); poly[styrene-graft-(poly(ethylene glycol) methyl ether)]-poly[3-[(methacrylate propylsulfonyl)(trifluoromethanesulfonyl)imide] sodium salt (PSPEG-NaAPTFSI); poly(ethylene oxide)-poly[4-styrenesulfonyl(trifluorosulfonylimide)] (PEO-PSTFSI); poly[poly(ethylene glycol) methyl ether acrylate]- poly[3-((trifluoromethane)sulfonamidosulfonyl)propyl methacrylate] (PEGMA-PAPTFSI); lithium poly(2-(trifluoromethyl)-N-[(trifluoromethyl)sulfonyl]-2- propenamide))-poly(ethylene oxide) vinyl ether; poly(ethylene oxide)- poly[3- ((trifluoromethane)sulfonamidosulfonyl)propyl methacrylate] (PEO-PAPTFSI); and lithium salt poly(ethylene oxide)-poly[(paraphenylene-oxyhexylsulfonyl)(trifluoromethanesulfonyl)imide] (LiPPC6TFSI). In some embodiments, the matrix is selected from a group consisting of PEO-ND 24-015 TFSI, PEO-LiBETI, PCL-PTMC-LiTFSI, PEO-LiPPC6TFSI, PEO-Mg(TFSI)2, PEO-NaClO4, and PEO-KBF4.

[0102] The ionic species and polymer of the matrix may be non-covalently or covalently bonded. In some embodiments, the matrix is non-covalently bonded and selected from the group consisting of PEO-TFSI, PEO-LiBETI, PCL-PTMC-LiTFSI, PEO-LiPPC6TFSI, PEO-Mg(TFSI)2, PEO-NaClO4, and PEO-KBF4. In some embodiments, the covalently bonded matrix may be selected from a group consisting of poly[poly(ethylene glycol) methyl ether acrylate]-poly[(4- styrenesulfonyl)(trifluoromethanesulfonyl)imide] lithium salt (PEGMA–LiPSTFSI), poly(ethylene oxide)-poly[4-styrenesulfonyl(trifluorosulfonylimide) potassium salt] (PEO-KPSTFSI), poly[styrene-graft-(poly(ethylene glycol) methyl ether)]-poly[3-[(methacrylate propylsulfonyl)(trifluoromethanesulfonyl)imide] sodium salt (PSPEG-NaAPTFSI), poly[poly(ethylene glycol) methyl ether acrylate]- poly[3- ((trifluoromethane)sulfonamidosulfonyl)propyl methacrylate] sodium salt (PEGMA-NaAPTFSI), poly(trimethylene carbonate)- poly[3-[(methacrylate propylsulfonyl)(trifluoromethanesulfonyl)imide] lithium salt (PTMC-LiAPTFSI), poly(methyl(cyclic [(allyloxy) methyl] ethylene ester carbonate)siloxane-poly(methyl(lithium tris(perfluorophenyl)(2,3,5,6-tetrafluoro-4-(2-(2-(oxy)ethoxy)ethoxy)phenyl) borate)siloxane, and crosslinked poly(ethylene glycol)-tetrakis(4−(chloromethyl)–2,3,5,6-tetrafluorophenyl)borate lithium salt.

[0103] In some embodiments, the electrolyte composite may be ionically conductive. In some embodiments the electrolyte composite may have an ionic conductivity of at least 10-5S / cm.

[0104] In some embodiments, the electrolyte composite may be electronically conductive. In some embodiments, the electrolyte composite may have an electronic conductivity of at least 10-5S / cm. In some embodiments, the electrolyte composite may have an electronic conductivity of at most 10-5S / cm.

[0105] In some embodiments, the electrolyte composite may have an ionic conductivity of at least 125% greater than the ionic conductivity of the matrix. In some embodiments, the electrolyte composite may have an ionic conductivity of at least 5%,10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, 105%, 110%, 115%, or 120% greater than the ionic conductivity of the matrix.

[0106] In some embodiments, the electrolyte composite may further comprise a dopant dispersed within the matrix containing a plurality of charge-transfer crystals. Typical methods of adding the dopant are known to those skilled in the art and can include mechanical mixing, vapor doping of a film containing the polymer and / or ionic species, and other doping methods known toND 24-015 those skilled in the art. In some embodiments, the dopant may be a solid. In some embodiments, the dopant may comprise inorganic particles, fibers, a scaffold, or plasticizer, or a combination thereof. Exemplary dopants include, but are not limited to SiO2, TiO2, Fe2O3, lithium lanthanum zirconium (LLZO), or lithium lanthanum titanium oxide (LLTO).

[0107] The electrolyte composites described herein may be used in an electrochemical cell. In some embodiments, an electrochemical cell may comprise a negative electrode, a positive electrode, and the electrolyte composites described herein. As used herein, “positive electrode” may be used interchangeably with the term “cathode.” The positive electrode may be positively charged. During discharge, the positive electrode may acquire electrons from the negative electrode. Conversely, during charging, the positively electrode may release electrons. The positive electrode may be any material known to a person of ordinary skill in the art that may behave as a positive electrode as described herein. Exemplary positive electrodes include, but are not limited to, lithium cobalt oxide (LCO), lithium nickel manganese cobalt oxide (NMC), lithium nickel cobalt aluminum oxide (NCA), lithium iron phosphate (LFP), lithium nickel manganese oxide (LNMO), sodium layered oxides (SLOs), NaVPO4F, potassium manganese hexacyanoferrate (KMF), Prussian blue (PB), and sulfur.

[0108] A “negative electrode,” as used herein, may be used interchangeably with the term “anode.” The negative electrode may be negatively charged. During discharge, the negative electrode may release electrodes that travel to the positive electrode. Conversely, during charging, the negative electrode may acquire electrons. The negative electrode may be any material known to a person of ordinary skill in the art that may behave as a negative electrode described herein. Exemplary negative electrodes that may be used in the electrochemical cells include, but are not limited to, lithium metal, sodium metal, potassium metal, magnesium metal, calcium metal, zinc metal, aluminum metal, iron, steel, silicon, graphite, carbon, tin oxide, and lithium titanate (LTO).

[0109] An electrochemical cell of the present disclosure may further comprise an electronically insulating material. In some embodiments, the electrolyte composite may be positioned between the negative electrode and the positive electrode. In some embodiments, an electronically insulating material may be positioned between the positive electrode and the electrolyte composite. In some embodiments, an electronically insulating material may be positioned between the negative electrode and the electrolyte composite. In some embodiments, an electronically insulating material may be positioned between both the positive and negative electrode and the electrolyte composite.ND 24-015

[0110] In some embodiments, the electronically insulating material between the positive electrode and the electrolyte composite may comprise the same materials as the electronically insulating material between the negative electrode and the electrolyte composite. In some embodiments, the electronically insulating material may comprise an inorganic electrolyte. In some embodiments, the electronically insulating material may comprise a polymer electrolyte. In some embodiments, the electronically insulating material may comprise an ionically conductive species, a cross-linked polymer, or a plasticizer. Any species that may be ionically conductive species may be used as the electronically insulating material, as long as the ionically conductive species possesses the same active ion as the electrolyte composite. For example, if lithium is used in the electrolyte composite as the transport ion, then any ionically conductive species used in the electronically insulating material should also include lithium. Exemplary cross-linked polymers that may be used as the electronically insulating material may be formed from monomers including, but are not limited to, ethylene glycol dimethacrylate, poly(ethylene glycol) diacrylate, poly(ethylene glycol) diglycidyl ether, and divinylbenzene. Any known plasticizer that increases ion mobility in polymer electrolytes may be used in the electronically insulating material. Examplary plasticizers include, but are not limited to, succinonitrile, poly(ethylene glycol) dimethyl ether, tetra(ethylene glycol) dimethyl ether, 4,7,10,13-tetraoxahexadecane-1,16-dinitrile, 1-butyl- 2,3-dimethylimidazolium bromide, and silica nanoparticles.

[0111] In some embodiments, the electronically insulating material may further comprise a porous support. In some embodiments, the porous support may be a glass fiber, porous polymer film, or a separator. In some embodiments, the porous support may be cellulose. Additional separators that may be used are known in the art and may be used in the electrochemical cell including the electrolyte composites described herein (see, e.g., Lagadec, M.F; Zahn, R.; and Wood, V. Characterization and performance evaluation of lithium-ion battery separators. Nat Energy 2019, 4, 16–25; and Choi, J. and Kim, P.J. A roadmap of battery separator development: past and future. Curr. Opin. Electrochem.2022, 31100858, each incorporated by reference in their entirety).

[0112] The assembly of the electrochemical cell may be performed by any means known to a person of ordinary skill in the art. One exemplary method is through ex-situ crosslinking at 85 °C for 1 hour. An additional exemplary method is through in-situ thermal crosslinking at 85 °C for 1 hour. Additional exemplary techniques that may be used to assemble the electrochemical cell include, but are not limited to, lamination. Hot pressing, extrusion, spray coating, electrospinning, and combinations thereof.ND 24-015

[0113] It will be apparent to those of ordinary skill in the relevant art that suitable modifications and adaptations to the methods, processes, and applications described herein can be made without departing from the scope of any embodiments or aspects thereof. The methods provided are exemplary and are not intended to limit the scope of any of the specified embodiments. All of the various embodiments, aspects, and options disclosed herein can be combined in any variations or iterations. The scope of the methods and processes described herein include all actual or potential combinations of embodiments, aspects, options, examples, and preferences herein described. The exemplary methods described herein may substitute any component disclosed herein, or include any component disclosed elsewhere herein. Should the meaning of any terms in any of the patents or publications incorporated by reference conflict with the meaning of the terms used in this disclosure, the meanings of the terms or phrases in this disclosure are controlling. Furthermore, the foregoing discussion discloses and describes merely exemplary embodiments. All patents and publications cited herein are incorporated by reference herein for the specific teachings thereof.

[0114] Various embodiments and aspects of the inventions described herein are summarized by the following clauses: Clause 1. An electrolyte composite comprising: a plurality of charge-transfer complex crystals dispersed within a matrix comprising an ionic species and a polymer, wherein the charge-transfer complex crystals comprise an organic electron accepting molecule and an organic electron donating molecule. Clause 2. The electrolyte composite of clause 1, wherein the composite is non-porous and solvent-free. Clause 3. The electrolyte composite of clause 1 or 2, wherein the matrix is non-crystalline and non-glassy. Clause 4. The electrolyte composite of any one of clauses 1–3, wherein the composite comprises: 10–50% by mass of charge-transfer complex crystals; and 50–90% by mass of the matrix. Clause 5. The electrolyte composite of any one of clauses 1–4, wherein the organic electron accepting molecule is selected from a group consisting of tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), and benzoquinone (BQ). Clause 6. The electrolyte composite of any one of clauses 1–5, wherein the organic electron donating molecule is selected from a group consisting of hydroquinone (HQ), phenoxazine (PX), thianthrene (TH), pyrene (PY), tetramethyltetraselenafulvalene (TMTSeF),ND 24-015 tetrathiafulvalene (TFF), hexamethylenetetraselenafulvalene (HMTTF), hexamethylenetetraselenafulvalene (HMTSF), and bis(ethylenedithio)tetrathiafulvalene (BEDT-TFF). Clause 7. The electrolyte composite of any one of clauses 1–6, wherein a charge-transfer crystal in the plurality of charge-transfer complex crystals has an electronic conductivity of at least 10−6S / cm prior to being used in the electrolyte composite. Clause 8. The electrolyte composite of any one of clauses 1–7, wherein the charge-transfer complex crystals have a neutral charge-transfer value or non-integer charge-transfer value. Clause 9. The electrolyte composite of clause 8, wherein the neutral charge-transfer value of zero. Clause 10. The electrolyte composite of clause 8, wherein the non-integer charge-transfer value is between 0 and 1. Clause 11. The electrolyte composite of any one of clauses 1–10, wherein the ionic species comprises a cation selected from a group consisting of lithium, sodium, potassium, calcium, magnesium, zinc, and aluminum. Clause 12. The electrolyte composite of any one of clauses 1–11, wherein the ion species further comprises an anion. Clause 13. The electrolyte composite of any one of clauses 1–12, wherein the anion comprises a sulfonate, a bis(sulfonyl)imide, derivatives thereof, and salts thereof. Clause 14. The electrolyte composite of any one of clauses 1–13, wherein the anion is selected from a group consisting of bis(pentafluoroethanesulfonyl)imide (BETI), bis(trifluoromethanesulfonyl)imide (TFSI), bis(fluorosulfonyl)imide (FSI), trifluoromethanesulfonate (TfO), and trifluoromethanesulfonate (TF). Clause 15. The electrolyte composite of any one of clauses 1–14, wherein the anion comprises a polyatomic anion. Clause 16. The electrolyte composite of any one of clauses 1–15, wherein the polyatomic anion is selected from a group consisting of ClO4−, BF4−, and PF6−. Clause 17. The electrolyte composite of any one of clauses 1–11, wherein the ionic species further comprises a polyanion. Clause 18. The electrolyte composite of any one of clauses 1–11 and clause 17, wherein the polyanion comprises a sulfonate, a bis(sulfonyl)imide, derivatives thereof, and salts thereof.ND 24-015 Clause 19. The electrolyte composite of any one of clauses 1–11 and clauses 17–18, wherein the polyanion comprises (4-styrenesulfonyl)(trifluoromethanesulfonyl)imide, derivatives thereof, and salts thereof. Clause 20. The electrolyte composite of any one of clauses 1–11 and clauses 17–19, wherein the polyanion is selected from a group consisting of poly[(4- styrenesulfonyl)(trifluoromethanesulfonyl)imide] (PSTFSI), poly[3-[(methacrylate propylsulfonyl)(trifluoromethanesulfonyl)imide] (PAPTFSI), and poly[((6-(2,5- dichlorophenoxy)hexyl)sulfonyl)-((trifluoromethyl)sulfonyl)amide] (PPC6TFSI). Clause 21. The electrolyte composite of any one of clauses 1–20, wherein the polymer is linear, branched, cross-linked, or a combination thereof. Clause 22. The electrolyte composite of any one of clauses 1–21, wherein the polymer comprises at least one polar polymer. Clause 23. The electrolyte composite of any one of clauses 1–21, wherein the polymer is a homopolymer comprising a polyether, a polyester, a polyacrylate, a polycarbonate, a polyketone, a polyurea, a poly(ionic liquid), a polythioether, a polythioester, a polythiocarbonate, a polythiourea, or a derivative thereof. Clause 24. The electrolyte composite of any one of clauses 1–21, wherein the polymer is a homopolymer comprising a polyethylene oxide, poly[poly(ethylene glycol) methyl ether acrylate] (PEGMA), or derivatives thereof; and salts thereof. Clause 25. The electrolyte composite of any one of clauses 1–21, wherein the polymer is a copolymer comprising one or more polar polymers. Clause 26. The electrolyte composite of any one of clauses 1–21 and clause 25, wherein the one or more polar polymers comprise a polyether, a polyester, a polyacrylate, a polycarbonate, a polyketone, a polyurea, a poly(ionic liquid), a polythioether, a polythioester, a polythiocarbonate, a polythiourea, derivatives thereof, or combinations thereof. Clause 27. The electrolyte composite of any one of clauses 1–21 and clauses 25–26, wherein the one or more polar polymers are selected from a group consisting of poly[poly(ethylene glycol) methyl ether acrylate] (PEGMA), a poly[poly(propylene glycol) methyl ether acrylate], a poly(ethylene oxide) (PEO), a poly[4-styrenesulfonyl(trifluorosulfonylimide)] (PS), a poly[3-((trifluoromethane)sulfonamidosulfonyl)propyl methacrylate], a poly(ε- caprolactone) (PCL), a poly(trimethylene carbonate) (PTMC), a poly(pentyl malonate), derivatives thereof, and combinations thereof.ND 24-015 Clause 28. The electrolyte composite of any one of clauses 1–21 and clauses 25–27, wherein the copolymer further comprises one or more non-polar polymers. Clause 29. The electrolyte composite of any one of clauses 1–21 and clauses 25–28, wherein the one or more non-polar polymers comprises a polyolefin, a fluoropolymer, an aromatic polymer, or derivatives thereof. Clause 30. The electrolyte composite of any one of clauses 1–21 and clauses 25–29, wherein the one or more non-polar polymers is selected from a group consisting of a polyethylene, a polyvinylidene difluoride, or a polystyrene. Clause 31. The electrolyte composite of any one of clauses 1–21 and clauses 25–30, the polymer is a copolymer selected from the group consisting of poly(ε-caprolactone)- poly(trimethylene carbonate) (PCL-PTMC), poly(ethylene oxide)-polystyrene (PEO-PS), derivatives thereof, and salts thereof. Clause 32. The electrolyte composite of any one of clauses 1–31, wherein the matrix is non- covalently associated. Clause 33. The electrolyte composite of claim 1–32, wherein the matrix selected from the group consisting of PEO-TFSI, PEO-LiBETI, PCL-PTMC-LiTFSI, PEO-LiPPC6TFSI, PEO-Mg(TFSI)2, PEO-NaClO4, and PEO-KBF4. Clause 34. The electrolyte composite of any one of clauses 1–31, wherein the matrix is covalently associated. Clause 35. The electrolyte composite of any one of clauses 1–31 and clause 34, wherein the matrix is selected from a group consisting of poly[poly(ethylene glycol) methyl ether acrylate]-poly[(4-styrenesulfonyl)(trifluoromethanesulfonyl)imide] lithium salt (PEGMA- LiPSTFSI). Clause 36. The electrolyte composite of any one of clauses 1–35, having an ionic conductivity of at least 10−5S / cm. Clause 37. The electrolyte composite of any one of clauses 1–36, having an electronic conductivity of at least 10−5S / cm. Clause 38. The electrolyte composite of any one of clauses 1–36, having an electronic conductivity of at most 10−5S / cm. Clause 39. The electrolyte composite of any one of clauses 1–38, having an ionic conductivity of at least 125% greater than the ionic conductivity of the matrix. Clause 40. The electrolyte composite of any one of clauses 1–39, further comprising a dopant. Clause 41. The electrolyte composite of clause 40, wherein the dopant comprises inorganic particles, fibers, a scaffold, or plasticizer, or a combination thereof.ND 24-015 Clause 42. An electrochemical cell comprising: a negative electrode; a positive electrode; and the electrolyte composite of any one of clauses 1–41 positioned between the negative electrode and the positive electrode. Clause 43. The electrochemical cell of clause 42, further comprising an electronically insulating material. Clause 44. The electrochemical cell of clauses 42 or 43, wherein the electronically insulating material is positioned between the positive electrode and the electrolyte composite, between the negative electrode and the electrolyte composite, or between both the positive and negative electrodes and the electrolyte composite. Clause 45. The electrochemical cell of any one of clauses 42–44, wherein the electronically insulating material between the positive electrode and the electrolyte composite comprises the same materials as the electronically insulating material between the negative electrode and the electrolyte composite. Clause 46. The electrochemical cell of any one of clauses 42–45, wherein the electronically insulating material comprises an ionically conductive species, a cross-linked polymer, or a plasticizer. Clause 47. The electrochemical cell of any one of clauses 42–46, wherein the electronically insulating material further comprises a porous support. EXAMPLES Example 1: Fabrication of Exemplary Electrolyte Composites in the Absence of Water Preparation of Exemplary of Charge Transfer Complexes

[0115] CT complex [TTF-TCNQ]: Tetrathiafulvalene (TTF, 100 mg, 0.49 mmol) and tetracyanoquinodimethane (TCNQ, 100 mg, 0.49 mmol) were each dissolved in 40 mL of anhydrous acetonitrile (CH3CN) at a concentration of 2.5 mg / ml, separately. Then at 60 °C, the TTF solution was added dropwise to the TCNQ solution over 30 min. After the mixed solution was cooled down to room temperature, the target solid [TTF-TCNQ] charge-transfer (CT) complex was obtained by vacuum filtration in accordance Wu, L.; Wu, F.; Sun, Q.; Shi, J.; Xie, A.; Zhu, X.; Dong, W. A TTF-TCNQ Complex: An Organic Charge-Transfer System with Extraordinary Electromagnetic Response Behavior. J. Mater. Chem.2021, 9 (9), 3316–3323, incorporated byND 24-015 reference in its entirety herein. The TTF-TCNQ CT complex was transferred into an argon glovebox and dried under vacuum at 75 °C for 24 hours to remove the remaining solvent.

[0116] CT complex [TMTSeF-TCNQ]: Tetramethyltetraselenafulvalene (TMTSeF, 40 mg, 0.089 mmol) was dissolved in 20 mL of dichloromethane. Tetracyanoquinodimethane (TCNQ, 18.23 mg, 0.089 mmol) was dissolved in 9.91 mL of anhydrous acetonitrile. The two solutions were mixed, and the glass vial containing the mixture was placed into an aluminum bead bath at 40 °C in an argon glovebox. The slowly evaporated over more than one week. The dark colored [TMTSeF-TCNQ] CT complex was dried under vacuum at 75 °C for 24 hours to remove the remaining solvent. Preparation of Exemplary Electrolyte Composites General Exemplary Synthesis of Electrolyte Composites

[0117] In an argon glovebox, polymer was dissolved in anhydrous CH3CN with a concentration of 200 mg / mL. Desired amounts of the polymer, CT complex, and the ionic species were stirred at room temperature. The resulting solution was drop-cast on a stainless-steel substrate. After most solvent evaporated in the glovebox, the composite electrolyte was dried in the vacuum oven in the glovebox at 75 °C for 24 hours to obtain the solid-state non-porous composite electrolytes (photograph in FIG.2). Samples were stored inside the argon glovebox until use.

[0118] Composite PEO-LiTFSI-[TTF-TCNQ]: This composite electrolyte was prepared following the general procedure above where PEO was used as the polymer, lithium bis(trifluoromethylsulfonyl)imide (LiTFSI, TCI Chemicals) was used as the ionic species, and TTF- TCNQ was used as the charge-transfer complex. Varying amounts of PEO were used to produce three composites containing PEO-LiTFSI-[TTF-TCNQ]. The resulting composites had a Polymer:Ionic Species:CT complex mass ratio of 1) 39:25:26; 2) 47:31:22; and 3) 53:35:12.

[0119] Composite PEO-LiBETI-[TTF-TCNQ]: This composite electrolyte was prepared following the general procedure above where PEO was used as the polymer, lithium bis(pentafluoroethanesulfonyl)amide (LiBETI, TCI Chemicals) was used as the ionic species, and TTF-TCNQ was used as the charge-transfer complex. The resulting composite had a Polymer:Ionic Species:CT complex mass ratio = 36:31:33.ND 24-015

[0120] Composite PCL-PTMC-LiTFSI-[TTF-TCNQ]: Copolymer poly(ε-caprolactone-co- trimethylene carbonate) (PCL-PTMC, 80:20 molar ratio, MW= 246, 000 – 338,000 g / mol) was synthesized as reported by Park, B.; Andersson, R.; Pate, S. G.; Liu, J.; O’Brien, C. P.; Hernández, G.; Mindemark, J.; Schaefer, J. L. Ion Coordination and Transport in Magnesium Polymer Electrolytes Based on Polyester-Co-Polycarbonate. Energy Mater. Adv. 2021, 2021, incorporated by reference in its entirety herein. The composite electrolyte was prepared following the general procedure above where PLC-PTMC was used as the polymer, lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) was used as the ionic species, and TTF-TCNQ was used as the charge-transfer complex. The resulting composite had a Polymer:Ionic Species:CT complex mass ratio = 61:16:23.

[0121] Composite PEO-Mg(TFSI)2-[TTF-TCNQ]: This composite electrolyte was prepared following the general procedure above where PEO was used as the polymer, magnesium bis(trifluoromethylsulfonyl)imide (Mg(TFSI)2(Solvionic) was used as the ionic species, and TTF- TCNQ was used as the charge-transfer complex. The resulting composite had a Polymer:Ionic Species:CT complex mass ratio = 47:31:22.

[0122] Composite PEO-NaClO4-[TTF-TCNQ]: This composite electrolyte was prepared following the general procedure above where PEO was used as the polymer, sodium perchlorate (NaClO4, Sigma Aldrich) was used as the ionic species, and TTF-TCNQ was used as the charge- transfer complex. The resulting composite had a Polymer:Ionic Species:CT complex mass ratio = 45:13:42.

[0123] Composite PEO-KBF4-[TTF-TCNQ]: This composite electrolyte was prepared following the general procedure above where PEO was used as the polymer, potassium tetrafluoroborate (KBF4, Sigma Aldrich) was used as the ionic species, and TTF-TCNQ was used as the charge-transfer complex. The resulting composite had a Polymer:Ionic Species:CT complex mass ratio = 62:9:29.

[0124] Composite PEO-LiPPC6TFSI-[TTF-TCNQ]: Lithiated ionomer lithium poly(((6-(2,5- dichlorophenoxy)hexyl)sulfonyl)-((trifluoromethyl)sulfonyl)amide) (LiPPC6TFSI) was synthesized in accordance Liu, J.; Yang, L.; Pickett, P.D.; Park, B.; and Schaefer, J.L. Li+Transport in Single- Ion Conducting Side-Chain Polymer Electrolytes with Nanoscale Self-Assembly of Ordered Domains. Macromolecules 2022, 55(17), 7752–7762, incorporated by reference in its entiretyND 24-015 herein. This composite electrolyte was prepared following the general procedure above where PEO was used as the polymer, LiPPC6TFSI was used as the ionic species, and TTF-TCNQ was used as the charge-transfer complex. The resulting composite had a Polymer:Ionic Species:CT complex mass ratio = 62:9:29.

[0125] Composite PEO-LiTFSI-[TMTSeF-TCNQ]: This composite electrolyte was prepared following the general procedure above where PEO was used as the polymer, LiTFSI was used as the ionic species, and TMTSeF-TCNQ was used as the charge-transfer complex. The resulting composite had a Polymer:Ionic Species:CT complex mass ratio = 31:19:50. Exemplary Preparation of Exemplary Electrolyte Composites with Covalently Associated Matrix

[0126] Composite PEGMA-LiPSTFSI-[TTF-TCNQ]: Random graft copolymer with tethered ionic groups (ionomer) PEGMA-LiPSTFSI was synthesized in accordance with methods described by Meziane, R.;Bonnet, J.-P.; Courty, M.; Djellab, K.; Armand, M. Single-Ion Polymer Electrolytes Based on a Delocalized Polyanion for Lithium Batteries. Electrochim. Acta 2011, 57, 14–19, incorporated by reference in its entirety herein. Briefly, polyethylene glycol methyl ether acrylate (Alfa Aesar, Mn = 5000 g / mol) was reacted with styrenesulfonyl(trifluoromethyl sulfonyl)imide potassium salt (KSTFSI, synthesized as described by Feng, S.; Shi, D.; Liu, F.; Zheng, L.; Nie, J.; Feng, W.; Huang, X.; Armand, M.; Zhou, Z. Single Lithium-Ion Conducting Polymer Electrolytes Based on Poly[(4-Styrenesulfonyl)(Trifluoromethanesulfonyl)Imide] Anions. Electrochim. Acta 2013, 93, 254–263, incorporated by reference herein). The resulting copolymer was found to have a repeating unit ratio of [PEGMA]:[LiPSTFSI] = 1:5.6 using1H NMR spectroscopy. The molecular structure of the copolymer is shown in FIG.3, where x = 5.6, y = 1, and n = 110. This composite electrolyte was prepared according to the general procedure shown above, with 100 mg / mL of PEGMA-LiPSTFSI and Ionomer:CT complex mass ratio = 75:25. Preparation of Electrolyte without CT complex

[0127] Pure polymer electrolyte (matrix) samples: Samples were prepared in an equivalent manner to the general procedure described above for each electrolyte composite, but with an equivalent mass ratio of Polymer:Ionic Species and without the addition of CT complex. Example 2: Characterization of the Electrolyte CompositesND 24-015 Exemplary Methods for Measuring Ionic Conductivity

[0128] In the argon glovebox, 2032 type coin cells (MTI Corp) were crimped with the solid- state electrolyte positioned between two stainless steel spacers (15.5 mm diameter × 0.2 mm thick) as electrodes. These electrodes were separated by a 100 μm-thick Teflon film ring that also served as the spacer to maintain the electrolyte thickness. Alternating current (AC) measurements were conducted on a Novocontrol Broadband Dielectric spectrometer equipped with an alpha-A high performance frequency analyzer and Quatro temperature control system with a cryostat. Data was collected on coin cells in a frequency range from 1 × 106Hz to 0.1 Hz at an AC voltage amplitude of 0.01 V. The temperature was decreased at 5 °C / min with 5 min of stabilization time at each measurement temperature. Ionic Conductivity of Solid Electrolyte Composite

[0129] Various types of conduction phenomena were observed in the AC measurement results. In some cases, only ionic conductivity was visible. In cases where both ionic conductivity and electronic conductivity were visible in the AC measurement results (mixed conduction phenomena), the spectra were fit to equivalent circuit models. When ionic conductivity exceeded electronic conductivity by less than 50 times, impedance data was found to fit to an equivalent circuit model as shown in FIG. 4. In cases where ionic conductivity exceeded electronic conductivity by more than 50 times and electronic conductivity was apparent, impedance data was found to fit to an equivalent circuit model as shown in FIG. 5. For either case, the ionic conductivity (^^^) is related to the ionic resistance (Ri) as follows: ^^^= d / (A*Ri) where d is the sample thickness and A is the sample area.

[0130] The ionic conductivity (σ୧,େ) of the exemplary solid-state electrolyte composites described in Example 1 as compared to control / matrix samples (σ୧,^) are summarized in Table 1. The percent change in conductivity for each composite relative to the matrix (lacking CT complex) is calculated as: ^^^^^^^^^^^^^^ ^^ℎ^^^^^^^^ ^%^ ൌఙ^,^ି ఙ^,ಾఙ^,ಾ ൈ 100%.Table 1. Summary of the increase in ionic conductivity of exemplary electrolyte composites comprising a CT complex dispersed in a matrix containing an ionic species (cation + anion) and a polymer Ionic olymer Species CT Complex Po Percent P l.-Ionic σi,Cσi,MChange (cation + Species-CT (S / cm) (S / cm) anion) in σi(%) -3TFSI 39-25-36 1 × 10 2 ×-51 PEO Li 10 4900ND 24-015 F-TCNQ] 47-31-22 2 × 10-4 -52 PEO LiTFSI [TT 2 × 10 at 25 °C at 25 °C 900 --comprising an ionomer and a CT complex nt e ) 0a e . ummary o e ncrease n onc con uc v y o exempary eecroye compos es comprising a CT complex dispersed in a matrix containing an ionic species (cation + polyanion) and a polymer Ionic Species Pol.-Ionic σ CT Complex Species-i,CσiPercent Polymer (cation +,M(S / cm) (S / cm Change polyanion) CT ) in σi(%) 6 × 10-77 × 10-1111 PEO LiPPC6TFSI [TFF-TCNQ] 64-6-30 at 25 °C at 25 °C 860000

[0131] The value of the real part of the complex conductivity (real conductivity) from the AC measurement at 0.1 Hz (σ'0.1Hz) for each composite electrolyte sample is displayed in Table 4. The frequency of 0.1 Hz was the lowest frequency for which the AC measurement was conducted. The electronic conductivity of a material is the value of the real conductivity at infinitely low frequency, since ion polarization reduces the contribution of ionic charges to the measured conductivity at low frequency. Therefore, the value of σ'0.1Hzis the maximum value possible for the electronic conductivity for the measured material. In instances where σ' is decreasing as frequency is decreased towards 0.1 Hz, then the electronic conductivity must be less than the value of σ'0.1Hz.ND 24-015 Table 4. Real conductivity of the composites at 0.1 Hz (σ'0.1Hz) Ratio of Real Conductivity at Electrolyte Composite Com onents 01 Hz (σ' )

[0132] A frequency range from 1 × 106Hz to 0.1 Hz at an AC voltage amplitude of 0.01 V was applied to the electrolyte composites and the temperature was ramped at 5 °C / min with 5 min of stabilization time at each measurement temperature. Temperature dependency of the ionic conductivity of electrolyte composites containing charge-transfer complexes are shown in FIG.6– 14. Also shown is a comparison between the electrolyte composite disclosed herein and polymer electrolyte without a charge transfer complex. Differential Scanning Calorimetry (DSC) of Exemplary Electrolyte Composites

[0133] The thermal transitions of the non-porous composite electrolyte PEO-LiTFSI-[TTF- TCNQ] in a ratio of 39-25-36 were monitored by differential scanning calorimetry (DSC) Q2000 (TA Instruments) under a nitrogen purge of 50 mL / min, with a heating / cooling rate of 5 °C / min and isothermal period of 2 min from -70 to 90 °C (results, FIG. 15). The glass transition temperatures of polymer-lithium salt-CT complex composite electrolyte and polymer-lithium salt blank sample are found to be -47 °C and -41 °C, respectively. The glass transition temperature was taken to be the midpoint of the transition in the heat flow versus temperature plot at low temperatures. Potential Li+Conduction Mechanism

[0134] Examination of the ionic conductivity for PEO-LiTFSI-[TCNQ-TFF] at a ratio of 39-25- 36 as a function of temperature normalized to the glass transition temperature showed a significant increase in ionic conductivity (FIG.16). This result shows that the enhancement of the conductivity of the electrolyte with the addition of CT complex may not be attributed to theND 24-015 depression of the glass transition temperature; the mechanism for the enhancement in conductivity may be unrelated to matrix segmental motion. This data indicates that a different ion conduction mechanism may be responsible for the increase in ionic conductivity when the CT complex is added to the polymer electrolyte matrix.

[0135] Additionally, the ionic conductivity of the composite electrolyte was fit to the curve (FIG. 17) by an equation that is the linear combination of the Arrhenius term and the Vogel-Fulcher-Tammann (VFT) term, ^^^െ^^^^^െ^^^^^^^^^ ^,^ ൌ ^^^^^^^^^ ^ ^^^^^^^^^െ^^0^, where ^^^,^is the ionic conductivity of the composite electrolyte, prefactor and activation energy in Arrhenius term, ^^ andand activation energy in the VFT ^^^is the Vogel temperature, ^^ is the universal gas constant, ^^ is the absolute measurement temperature. The experimental data generated with PEO-LiTFSI-[TCNQ-TFF] at a ratio of 39-25- 36 fit the data generated from the equation that is the linear combination of the Arrhenius term and the VFT term (FIG.17). This result further supports that lithium conduction likely occurs on the surface of crystals as opposed to being induced by only by the segmental motion of the polymer chains, which is the typical mechanism for PEO-based electrolytes that results in VFT behavior at temperatures above the crystallization temperature. Scanning Electron Microscopy (SEM) of Exemplary Electrolyte Composites

[0136] Both pure CT complex samples and composite electrolyte PEO-LiTFSI-[TCNQ-TFF] at a ratio of 39-25-36 were transferred onto carbon tapes in the glovebox and transported to the SEM facility via a PELCO vacuum pin stub holder to minimize ambient air exposure. SEM images were collected using a Magellan 400 FESEM. The CT complex is solid crystalline particles, with square rod-like shape. The composite electrolyte was found to be dense, with the CT complex and polymer electrolyte existing as separate phases. Images are shown in FIG.18–20. State of Charge-Transfer Complex inside the Electrolyte Composite

[0137] Inside an argon glovebox, composite electrolyte PEO-LiTFSI-[TCNQ-TFF] at a ratio of 39-25-36 and its components pure CT complex [TTF-TCNQ] and matrix PEO-LiTFSI were each loaded into capillaries and sealed. XRD data was collected using a Bruker D8 Venture with a copper Diamond microfocus X-ray source and a Photon-III CMOS Area detector. Data were recorded using a composite of two phi-360 rotation images counted for 60 seconds per image at a sample-to-detector distance of 100 mm and then integrated across an angular range of 5 to 60ND 24-015 degrees in 2-theta. FIG.21 exhibits features apparent in the profiles of the pure components and shows the crystalline nature of the CTCs in the composite electrolyte. Example 3: Implementation of Exemplary Electrolyte Composites into Electrochemical Cells Exemplary Methods for Fabricating an Electrochemical Cell

[0138] A tri-layer electrolyte including the solid composite as the central layer was fabricated to reduce the electronic conduction through the tri-layer electrolyte (see schematic, FIG.22–23). An electronically insulating, protective polymer layer was applied on either side of the composite electrolyte PEO-LiTFSI-[TCNQ-TFF] at a ratio of 39-25-36 at the interfaces with electrodes via the procedure as follows. In an argon glovebox, a precursor solution for the protective crosslinked polymer layer (CPL) was prepared by adding 10.7 mg 2,2’-azobis(2-methylpropionitrile) (polymerization initiator), 238.1 mg succinonitrile, and 285.7 mg LiTFSI. Then 101 μL ethylene acrylate, 297 μL poly(ethylene glycol) diacrylate (PEGDA, average Mn 700), and 32 μL fluoroethylene carbonate were added to fully dissolve SN and LiTFSI. The precursor was dropped on the surface of electrodes, and the CT complex polymer electrolyte film was sandwiched between them. Then, after crimping, the precursor was in-situ crosslinked at 85 °C for 1 hour in the cell to result in the freestanding tri-layer configuration CPL / CT complex polymer electrolyte / CPL. In addition, the cellulose-based tri-layer configuration was prepared wherein a cellulose-based porous separator (diameter 10 mm, thickness 20 μm, and porosity 45%) was placed on each electrode. The precursor was dropped on the surface of separators to fill the pores, and the CT complex polymer electrolyte film was sandwiched between them. Then, after crimping, the precursor was in-situ crosslinked at 85 °C for 1 hour in the cell to result in the cellulose-based tri-layer configuration. This methodology was applied regardless of electrode type. Characterization of Electrochemical Cells

[0139] Symmetric electrochemical cells with stainless steel electrodes were used for frequency-dependent conduction characterization. Alternating current (AC) measurements were conducted on a Novocontrol Broadband Dielectric spectrometer equipped with an alpha-A high performance frequency analyzer and Quatro temperature control system with a cryostat. Data was collected on coin cells in a frequency range from 1 × 106Hz to 0.1 Hz at an AC voltage amplitude of 0.01 V. The temperature was decreased at 5 °C / min with 5 min of stabilization timeND 24-015 at each measurement temperature. The real part of the complex conductivity (conductivity’) for the tri-layer electrolyte (labeled CPL / CTPE / CPL) in a symmetric stainless steel cell varies significantly from that of the base composite electrolyte PEO-LiTFSI-[TCNQ-TFF] at a ratio of 39- 25-36 (see FIG.24) The tri-layer configuration significantly depresses the real part of the complex conductivity at low frequency, which is evidence that the electronic conductivity is significantly depressed and must be less than 5 x 10-7S / cm.

[0140] Ionic conductivity of the tri-layer composites were determined in the same manner as with the pure composite electrolytes. Both tri-layer configurations, freestanding and cellulose- based, simultaneously result in good ionic conductivity as a function of temperature (see FIG.25). The free-standing configuration achieves higher ionic conductivity than the cellulose-based tri- layer over most of the investigated temperature range.

[0141] Symmetric electrochemical cells with lithium metal electrodes were used for characterization of the interfacial resistance of the freestanding tri-layer electrolyte in contact with lithium metal. Alternating current (AC) electrochemical impedance spectroscopy (EIS) measurements were conducted in a frequency range from 1 × 106Hz to 1 Hz at an AC voltage amplitude of 0.01 V at room temperature. It is observable from the width of the curve in the impedance spectrum (see FIG.26) that the interfacial resistance is on the order of a few thousand ohms and is relatively stable from one to eight days.

[0142] Symmetric electrochemical cells with lithium metal electrodes and the composite electrolytes were galvanostatically cycled at room temperature using a Neware Battery Testing System at various current densities for 1 hr in each direction with a compliance voltage window of -5 V to +5 V (vs. Li+ / Li). The freestanding tri-layer composite electrolyte exhibited stable overpotential for lithium metal cycling (see FIG. 27 and 28) and relatively lower overpotential compared with the base composite electrolyte PEO-LiTFSI-[TCNQ-TFF] at a ratio of 39-25-36 (see FIG.28).

Claims

ND 24-015 CLAIMS What is claimed:

1. An electrolyte composite comprising: a plurality of charge-transfer complex crystals dispersed within a matrix comprising an ionic species and a polymer, wherein the charge-transfer complex crystals comprise an organic electron accepting molecule and an organic electron donating molecule.

2. The electrolyte composite of claim 1, wherein the composite is non-porous and solvent- free.

3. The electrolyte composite of claim 1, wherein the matrix is non-crystalline and non-glassy.

4. The electrolyte composite of claim 1, wherein the composite comprises: 10–50% by mass of charge-transfer complex crystals; and 50–90% by mass of the matrix.

5. The electrolyte composite of claim 1, wherein the organic electron accepting molecule is selected from a group consisting of tetracyanoquinodimethane (TCNQ), 2,3-dichloro-5,6- dicyano-1,4-benzoquinone (DDQ), and benzoquinone (BQ).

6. The electrolyte composite of claim 1, wherein the organic electron donating molecule is selected from a group consisting of hydroquinone (HQ), phenoxazine (PX), thianthrene (TH), pyrene (PY), tetramethyltetraselenafulvalene (TMTSeF), tetrathiafulvalene (TFF), hexamethylenetetraselenafulvalene (HMTTF), hexamethylenetetraselenafulvalene (HMTSF), and bis(ethylenedithio)tetrathiafulvalene (BEDT-TFF).

7. The electrolyte composite of claim 1, wherein a charge-transfer crystal in the plurality of charge-transfer complex crystals has an electronic conductivity of at least 10−6S / cm prior to being used in the electrolyte composite.

8. The electrolyte composite of claim 1, wherein the charge-transfer complex crystals have a neutral charge-transfer value or non-integer charge-transfer value.ND 24-015 9. The electrolyte composite of claim 8, wherein the neutral charge-transfer value of zero.

10. The electrolyte composite of claim 8, wherein the non-integer charge-transfer value is between 0 and 1.

11. The electrolyte composite of claim 1, wherein the ionic species comprises a cation selected from a group consisting of lithium, sodium, potassium, calcium, magnesium, zinc, and aluminum.

12. The electrolyte composite of claim 11, wherein the ion species further comprises an anion.

13. The electrolyte composite of claim 12, wherein the anion comprises a sulfonate, a bis(sulfonyl)imide, derivatives thereof, and salts thereof.

14. The electrolyte composite of claim 12, wherein the anion is selected from a group consisting of bis(pentafluoroethanesulfonyl)imide (BETI), bis(trifluoromethanesulfonyl)imide (TFSI), bis(fluorosulfonyl)imide (FSI), trifluoromethanesulfonate (TfO), and trifluoromethanesulfonate (TF).

15. The electrolyte composite of claim 12, wherein the anion comprises a polyatomic anion.

16. The electrolyte composite of claim 15, wherein the polyatomic anion is selected from a group consisting of ClO4−, BF4−, and PF6−.

17. The electrolyte composite of claim 11, wherein the ionic species further comprises a polyanion.

18. The electrolyte composite of claim 17, wherein the polyanion comprises a sulfonate, a bis(sulfonyl)imide, derivatives thereof, and salts thereof.

19. The electrolyte composite of claim 17, wherein the polyanion comprises (4- styrenesulfonyl)(trifluoromethanesulfonyl)imide, derivatives thereof, and salts thereof.ND 24-015 20. The electrolyte composite of claim 17, wherein the polyanion is selected from a group consisting of poly[(4-styrenesulfonyl)(trifluoromethanesulfonyl)imide] (PSTFSI), poly[3- [(methacrylate propylsulfonyl)(trifluoromethanesulfonyl)imide] (PAPTFSI), and poly[((6- (2,5-dichlorophenoxy)hexyl)sulfonyl)-((trifluoromethyl)sulfonyl)amide] (PPC6TFSI).

21. The electrolyte composite of claim 1, wherein the polymer is linear, branched, cross- linked, or a combination thereof.

22. The electrolyte composite of claim 1, wherein the polymer comprises at least one polar polymer.

23. The electrolyte composite of claim 1, wherein the polymer is a homopolymer comprising a polyether, a polyester, a polyacrylate, a polycarbonate, a polyketone, a polyurea, a poly(ionic liquid), a polythioether, a polythioester, a polythiocarbonate, a polythiourea, or a derivative thereof.

24. The electrolyte composite of claim 1, wherein the polymer is a homopolymer comprising a polyethylene oxide, poly[poly(ethylene glycol) methyl ether acrylate] (PEGMA), or derivatives thereof; and salts thereof.

25. The electrolyte composite of claim 1, wherein the polymer is a copolymer comprising one or more polar polymers.

26. The electrolyte composite of claim 25, wherein the one or more polar polymers comprise a polyether, a polyester, a polyacrylate, a polycarbonate, a polyketone, a polyurea, a poly(ionic liquid), a polythioether, a polythioester, a polythiocarbonate, a polythiourea, derivatives thereof, or combinations thereof.

27. The electrolyte composite of claim 25, wherein the one or more polar polymers are selected from a group consisting of poly[poly(ethylene glycol) methyl ether acrylate] (PEGMA), a poly[poly(propylene glycol) methyl ether acrylate], a poly(ethylene oxide) (PEO), a poly[4-styrenesulfonyl(trifluorosulfonylimide)] (PS), a poly[3- ((trifluoromethane)sulfonamidosulfonyl)propyl methacrylate], a poly(ε-caprolactone)ND 24-015 (PCL), a poly(trimethylene carbonate) (PTMC), a poly(pentyl malonate), derivatives thereof, and combinations thereof.

28. The electrolyte composite of claim 25, wherein the copolymer further comprises one or more non-polar polymers.

29. The electrolyte composite of claim 28, wherein the one or more non-polar polymers comprises a polyolefin, a fluoropolymer, an aromatic polymer, or derivatives thereof.

30. The electrolyte composite of claim 28, wherein the one or more non-polar polymers is selected from a group consisting of a polyethylene, a polyvinylidene difluoride, or a polystyrene.

31. The electrolyte composite of claim 1, wherein the polymer is a copolymer selected from the group consisting of poly(ε-caprolactone)-poly(trimethylene carbonate) (PCL-PTMC), poly(ethylene oxide)-polystyrene (PEO-PS), derivatives thereof, and salts thereof.

32. The electrolyte composite of claim 1, wherein the matrix is non-covalently bonded.

33. The electrolyte composite of claim 32, wherein the matrix selected from the group consisting of PEO-TFSI, PEO-LiBETI, PCL-PTMC-LiTFSI, PEO-LiPPC6TFSI, PEO- Mg(TFSI)2, PEO-NaClO4, and PEO-KBF4.

34. The electrolyte composite of claim 1, wherein the matrix is covalently associated.

35. The electrolyte composite of claim 34, wherein the matrix is selected from a group consisting of poly[poly(ethylene glycol) methyl ether acrylate]-poly[(4- styrenesulfonyl)(trifluoromethanesulfonyl)imide] lithium salt (PEGMA-LiPSTFSI).

36. The electrolyte composite of claim 1, having an ionic conductivity of at least 10−5S / cm.

37. The electrolyte composite of claim 1, having an electronic conductivity of at least 10−5S / cm.ND 24-015 38. The electrolyte composite of claim 1, having an electronic conductivity of at most 10−5S / cm.

39. The electrolyte composite of claim 1, having an ionic conductivity of at least 125% greater than the ionic conductivity of the matrix.

40. The electrolyte composite of claim 1, further comprising a dopant.

41. The electrolyte composite of claim 40, wherein the dopant comprises inorganic particles, fibers, a scaffold, or plasticizer, or a combination thereof.

42. An electrochemical cell comprising: a negative electrode; a positive electrode; and the electrolyte composite of claim 1 positioned between the negative electrode and the positive electrode.

43. The electrochemical cell of claim 42, further comprising an electronically insulating material.

44. The electrochemical cell of claim 43, wherein the electronically insulating material is positioned between the positive electrode and the electrolyte composite, between the negative electrode and the electrolyte composite, or between both the positive and negative electrodes and the electrolyte composite.

45. The electrochemical cell of claim 43, wherein the electronically insulating material between the positive electrode and the electrolyte composite comprises the same materials as the electronically insulating material between the negative electrode and the electrolyte composite.

46. The electrochemical cell of claim 43, wherein the electronically insulating material comprises an ionically conductive species, a cross-linked polymer, or a plasticizer.ND 24-015 47. The electrochemical cell of claim 43, wherein the electronically insulating material further comprises a porous support.

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