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WO2025111549A1 - Composites d'électrolyte non poreux - Google Patents

Composites d'électrolyte non poreux Download PDF

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Publication number
WO2025111549A1
WO2025111549A1 PCT/US2024/057080 US2024057080W WO2025111549A1 WO 2025111549 A1 WO2025111549 A1 WO 2025111549A1 US 2024057080 W US2024057080 W US 2024057080W WO 2025111549 A1 WO2025111549 A1 WO 2025111549A1
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electrolyte composite
poly
electrolyte
composite
polymer
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Jennifer L. SCHAEFER
Lingyu Yang
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University of Notre Dame
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University of Notre Dame
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0065—Solid electrolytes
    • H01M2300/0082—Organic polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • 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.
  • 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).
  • Tg glass-transition temperatures
  • 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.
  • 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.
  • the composite is non-porous and solvent-free.
  • the matrix is non-crystalline and non-glassy.
  • the composite comprises:10– 50% by mass of charge-transfer complex crystals; and 50–90% by mass of the matrix.
  • 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).
  • 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).
  • HQ hydroquinone
  • PX phenoxazine
  • TH thianthrene
  • PY pyrene
  • TMTSeF tetramethyltetraselenafulvalene
  • TFT tetrathiafulvalene
  • TTFF tetrathiafulvalene
  • HMTTF hexamethylenetetra
  • a charge-transfer crystal in the plurality of charge-transfer complex crystals has an electronic conductivity of at least 10 ⁇ 6 S/cm prior to being used in the electrolyte composite.
  • 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.
  • 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.
  • the anion comprises a sulfonate, a bis(sulfonyl)imide, derivatives thereof, and salts thereof.
  • 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).
  • the anion comprises a polyatomic anion.
  • the polyatomic anion is selected from a group consisting of ClO 4 ⁇ , BF 4 ⁇ , and PF 6 ⁇ .
  • the ionic species further comprises a polyanion.
  • the polyanion comprises a sulfonate, a bis(sulfonyl)imide, derivatives thereof, and salts thereof.
  • the polyanion comprises (4-styrenesulfonyl)(trifluoromethanesulfonyl)imide, derivatives thereof, and salts thereof.
  • 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).
  • the polymer is linear, branched, cross-linked, or a combination thereof.
  • the polymer comprises at least one polar polymer.
  • 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.
  • the polymer is a homopolymer comprising a polyethylene oxide, poly[poly(ethylene glycol) methyl ether acrylate] (PEGMA), or derivatives thereof; and salts thereof.
  • the polymer is a copolymer comprising one or more polar polymers.
  • 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.
  • 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( ⁇ -caprolactone) (PCL), a poly(trimethylene carbonate) (PTMC), a poly(pentyl malonate), derivatives thereof, and combinations thereof.
  • PEGMA poly[poly(ethylene glycol) methyl ether acrylate]
  • PEO poly(ethylene oxide)
  • PS poly[4-styrenesulfonyl(trifluorosulfonylimide)]
  • PS poly[3
  • the copolymer further comprises one or more non- polar polymers.
  • the one or more non-polar polymers comprises a polyolefin, a fluoropolymer, an aromatic polymer, or derivatives thereof.
  • the one or more non-polar polymers is selected from a group consisting of a polyethylene, a polyvinylidene difluoride, or a polystyrene.
  • the polymer is a copolymer selected from the group consisting of poly( ⁇ -caprolactone)-poly(trimethylene carbonate) (PCL- PTMC), poly(ethylene oxide)-polystyrene (PEO-PS), derivatives thereof, and salts thereof.
  • the matrix is non-covalently bonded.
  • the matrix selected from the group consisting of PEO-TFSI, PEO-LiBETI, PCL-PTMC-LiTFSI, PEO-LiPPC6TFSI, PEO-Mg(TFSI) 2 , PEO-NaClO 4 , and PEO-KBF 4 .
  • the matrix is covalently associated.
  • 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).
  • the electrolyte composites has an ionic conductivity of at least 10 ⁇ 5 S/cm. In some embodiments, the electrolyte composites has an electronic conductivity of at least 10 ⁇ 5 S/cm. In some embodiments, the electrolyte composites has an electronic conductivity ND 24-015 of at most 10 ⁇ 5 S/cm.
  • the electrolyte composite has an ionic conductivity of at least 125% greater than the ionic conductivity of the matrix.
  • the electrolyte composite further comprises a dopant.
  • the dopant comprises inorganic particles, fibers, a scaffold, or plasticizer, or a combination thereof.
  • 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.
  • the electrochemical cell further comprises an electronically insulating material.
  • 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.
  • 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.
  • the electronically insulating material comprises an ionically conductive species, a cross-linked polymer, or a plasticizer.
  • the electronically insulating material further comprises a porous support.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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).
  • FIG.7 shows a graph of ionic conductivity as a function of temperature for PEO-LiBETI in the presence and absence of [TTF-TCNQ].
  • 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].
  • FIG. 9 shows a graph of ionic conductivity as a function of temperature for PEGMA- LiPSTFSI in the presence and absence of [TTF-TCNQ].
  • FIG. 10 shows a graph of ionic conductivity as a function of temperature for PEO- Mg(TFSI) 2 in the presence and absence of [TTF-TCNQ].
  • FIG. 11 shows a graph of ionic conductivity as a function of temperature for PEO- NaClO 4 in the presence and absence of [TTF-TCNQ].
  • FIG.12 shows a graph of ionic conductivity as a function of temperature for PEO-KBF 4 in the presence and absence of [TTF-TCNQ].
  • FIG.13 shows a graph of ionic conductivity as a function of temperature for PEO-LiTFSI in the presence and absence of [TMTSeF-TCNQ].
  • FIG. 14 shows a graph of ionic conductivity as a function of temperature for PEO- LiPPC6TFSI in the presence and absence of [TTF-TCNQ].
  • 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.
  • 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.
  • Tg/T glass transition temperature
  • 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.
  • 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.
  • 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.
  • 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].
  • XRD X-ray diffraction
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • “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.
  • alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, 2-propoxy, butoxy and tert-butoxy.
  • alkyl as used herein, means a straight or branched, saturated hydrocarbon chain.
  • lower alkyl or “C 1-6 alkyl” means a straight or branched chain hydrocarbon containing from 1 to 6 carbon atoms.
  • C 1-4 alkyl means a straight or branched chain hydrocarbon containing from 1 to 4 carbon atoms.
  • 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.
  • alkenyl means a straight or branched, hydrocarbon chain containing at least one carbon-carbon double bond.
  • alkoxyalkyl refers to an alkoxy group, as defined herein, appended to the parent molecular moiety through an alkyl group, as defined herein.
  • alkylamino means at least one alkyl group, as defined herein, is appended to the parent molecular moiety through an amino group, as defined herein.
  • amide means –C(O)NR– or –NRC(O)–, wherein R may be hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, alkenyl, or heteroalkyl.
  • 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.
  • amino means —NR x R y , wherein R x and R y may be hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, alkenyl, or heteroalkyl.
  • R x and R y may be hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, alkenyl, or heteroalkyl.
  • amino may be – NR x –, wherein R x may be hydrogen, alkyl, cycloalkyl, aryl, heteroaryl, heterocycle, alkenyl, or heteroalkyl.
  • aryl 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).
  • 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).
  • cyanoalkyl means at least one –CN group, is appended to the parent molecular moiety through an alkylene group, as defined herein.
  • ND 24-015 refers to a cycloalkyl group, as defined herein, appended to the parent molecular moiety through an oxygen atom.
  • cycloalkyl or “cycloalkane,” as used herein, refers to a saturated ring system containing all carbon atoms as ring members and zero double bonds.
  • 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).
  • a monocyclic cycloalkyl e.g., cyclopropyl
  • a fused bicyclic cycloalkyl e.g., decahydronaphthalenyl
  • 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).
  • cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, and bicyclo[1.1.1]pentanyl.
  • 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.
  • 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.
  • 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.
  • cycloalkylene and heterocyclylene refer to divalent groups derived from the base ring, i.e., cycloalkane, heterocycle.
  • an example cycloalkylene may be cyclohexene or and a heterocyclylene may .
  • Cycloalkylene and heterocyclylene include a groups such as 1,1- A further example is 1,1- cyclopropylene.
  • halogen or “halo,” as used herein, means Cl, Br, I, or F.
  • haloalkyl 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.
  • haloalkoxy means at least one haloalkyl group, as defined herein, is appended to the parent molecular moiety through an oxygen atom.
  • halocycloalkyl means a cycloalkyl group, as defined herein, in which one or more hydrogen atoms are replaced by a halogen.
  • heteroalkyl 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.
  • heteroaryl refers to an aromatic monocyclic heteroatom- containing ring (monocyclic heteroaryl) or a bicyclic ring system containing at least one monocyclic heteroaromatic ring (bicyclic heteroaryl).
  • 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., 10 ⁇ 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 fused bicyclic heteroaromatic ring system i.e., 10 ⁇ electron system
  • a monocyclic heteroaryl ring fused to a 6-membered arene e.g., quinolin-4-yl, indol-1-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 10 ⁇ 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.
  • 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
  • heterocycle or “heterocyclic,” as used herein, means a monocyclic heterocycle, a bicyclic heterocycle, or a tricyclic heterocycle.
  • 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.
  • 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, pyrazolin
  • 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.
  • bicyclic heterocyclyl is attached to the parent molecular moiety at a non- aromatic ring atom (e.g., indolin-1-yl).
  • 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, octa
  • 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.
  • 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.
  • hydroxyl or “hydroxy,” as used herein, means an —OH group.
  • hydroxyalkyl means at least one –OH group, is appended to the parent molecular moiety through an alkylene group, as defined herein.
  • 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., “C 1-4 alkyl,” “C 3- 6 cycloalkyl,” “C 1-4 alkylene”). These designations are used as generally understood by those skilled in the art.
  • C 3 alkyl is an alkyl group with three carbon atoms (i.e., n-propyl, isopropyl).
  • C 1-4 alkyl is an alkyl group having from 1 to 4 carbon atoms, however arranged (i.e., straight chain or branched).
  • substituted refers to a group that may be further substituted with one or more non-hydrogen substituent groups.
  • the electrolyte composites of the present disclosure comprise a plurality of charge-transfer complex crystals dispersed within a matrix comprising an ionic species and a ND 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the electrolyte composites of the present disclosure may be non-porous, solvent-free, or a combination of non-porous and solvent-free.
  • 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.
  • 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).
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • EMC ethyl methyl carbonate
  • EMC 1,2- dimethyloxyethane
  • FEC 1,3-dioxolane
  • DOL 1,3-dioxolane
  • MeOH acetonitrile
  • the electrolyte composites of the present disclosure may be solid.
  • 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.
  • amorphous may be used interchangeable with “non-crystalline” and is characterized by being substantially free of crystalline structures.
  • the electrolyte composites may be semi-crystalline.
  • the matrix in which a plurality of charge-transfer complex crystals may be dispersed may also be a solid.
  • 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 flexibility ND 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.
  • thermal energy in the glassy state of a polymer, there is no segmental motion of the polymer.
  • non-glassy 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.
  • non-glassy describes instances where a polymer with some degree of segmental is completely non-glassy and partially non-glassy.
  • the matrix of the electrolyte composite is non-glassy.
  • the matrix of the electrolyte composite is partially non-glassy.
  • the electrolyte composite may comprise about 10 % to about 50% by mass of charge-transfer complex crystals.
  • 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.
  • 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.
  • 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.
  • 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.
  • the electrolyte composite may comprise no greater than 90% by mass, no greater than 85% by mass, no greater than 80% by ND 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.
  • 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.
  • 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).
  • TCNQ tetracyanoquinodimethane
  • DDQ 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
  • BQ benzoquinone
  • 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).
  • HQ hydroquinone
  • PX phenoxazine
  • TH thianthrene
  • PY pyrene
  • TEZ tetrathiafulvalene
  • HMTTF hexamethylenetetraselenafulvalene
  • HMTSF hexamethylenetetraselenafulvalene
  • BEDT-TFF bis(ethylenedithio)tetrathiafulvalene
  • ionic conductivity is characterized by the mobility of at least one charged ion in a system.
  • Electric conductivity 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.
  • 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.
  • 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.
  • the matrix of the electrolyte composite may comprise an ionic species.
  • the ionic species is a cation.
  • the cation may be selected from a group consisting of lithium, sodium, potassium, calcium, magnesium, zinc, and aluminum.
  • the ionic species may further comprise an anion.
  • the anion may comprise a sulfonate, a bis(sulfonyl)imide, derivatives thereof, and salts thereof.
  • 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., M
  • 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).
  • 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).
  • the anion may comprise a polyatomic anion.
  • 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, but ND 24-015 are not limited to, ClO 4 ⁇ , BF 4 ⁇ , PF 6 ⁇ , SO 4 2 ⁇ , SO 3 2 ⁇ , CH 3 COO ⁇ , ClO 3 ⁇ , PO 4 3 ⁇ , PO 3 3 ⁇ , NO 3 ⁇ , and NO 2 ⁇ .
  • the polyatomic anion may be selected from a group consisting of ClO 4 ⁇ , BF 4 ⁇ , and PF 6 ⁇ .
  • the ionic species further comprises a polyanion.
  • 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.”
  • the polymer may be a copolymer.
  • the substituent bearing the negative charge may exist as a salt with an additional cation.
  • 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.
  • 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.
  • 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).
  • PSTFSI poly[(4-styrenesulfonyl)(trifluoromethanesulfonyl)imide]
  • PAPTFSI poly[3-[(methacrylate propylsulfonyl)(trifluoromethanesulfonyl)imide]
  • PPC6TFSI poly[(6-(2,5-dichlorophenoxy)hexyl)
  • 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.
  • the matrix of the electrolyte may comprise a polymer.
  • the polymer may be linear, branched, cross-linked, or a combination thereof.
  • the polymer may comprise at least one polar polymer.
  • 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.
  • 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( ⁇ -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.
  • PEO / PEG poly(ethylene glycol)
  • PPEGMEA poly[poly(ethylene glycol) methyl ether
  • the polymer may be a homopolymer comprising polyethylene oxide or derivatives thereof.
  • the polymer may be a copolymer.
  • the copolymer may comprise one or more polar polymers.
  • 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.
  • 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( ⁇ -caprolactone) (PCL), a poly(trimethylene carbonate) (PTMC), a poly(pentyl malonate), derivatives thereof, and combinations thereof.
  • PPEGMEA poly[poly(ethylene glycol) methyl ether acrylate]
  • PEO poly(ethylene oxide)
  • PSTFSI poly[4- styrenesulfonyl(trifluorosulfon
  • the copolymer may comprise one or more non-polar polymers.
  • the one or more non-polar polymers may comprise a polyolefin, a fluoropolymer, an aromatic polymer, or combinations thereof.
  • the one or more non-polar polymers may be selected from a group consisting of a polyethylene, a polyvinylidene difluoride, or a polystyrene.
  • the copolymer may comprise two differ polar polymers.
  • the copolymer may comprise at least one polar polymer and a non-polar polymer.
  • 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( ⁇ -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) diglycidal
  • 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.
  • 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)(trifluoro
  • 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-NaClO 4 , and PEO-KBF 4 .
  • the ionic species and polymer of the matrix may be non-covalently or covalently bonded.
  • 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-NaClO 4 , and PEO-KBF 4 .
  • 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
  • the electrolyte composite may be ionically conductive. In some embodiments the electrolyte composite may have an ionic conductivity of at least 10 -5 S/cm. [00104] 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- 5 S/cm. In some embodiments, the electrolyte composite may have an electronic conductivity of at most 10 -5 S/cm. [00105] In some embodiments, the electrolyte composite may have an ionic conductivity of at least 125% greater than the ionic conductivity of the matrix.
  • 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.
  • the electrolyte composite may further comprise a dopant dispersed within the matrix containing a plurality of charge-transfer crystals.
  • the dopant may be a solid.
  • the dopant may comprise inorganic particles, fibers, a scaffold, or plasticizer, or a combination thereof.
  • Exemplary dopants include, but are not limited to SiO 2 , TiO 2 , Fe 2 O 3 , lithium lanthanum zirconium (LLZO), or lithium lanthanum titanium oxide (LLTO).
  • the electrolyte composites described herein may be used in an electrochemical cell.
  • an electrochemical cell may comprise a negative electrode, a positive electrode, and the electrolyte composites described 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), NaVPO 4 F, potassium manganese hexacyanoferrate (KMF), Prussian blue (PB), and sulfur.
  • LCO lithium cobalt oxide
  • NMC lithium nickel manganese cobalt oxide
  • NCA lithium nickel cobalt aluminum oxide
  • LFP lithium iron phosphate
  • LNMO lithium nickel manganese oxide
  • SLOs sodium layered oxides
  • NaVPO 4 F potassium manganese hexacyanoferrate
  • KMF potassium manganese hexacyanoferrate
  • PB Prussian blue
  • 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).
  • An electrochemical cell of the present disclosure may further comprise an electronically insulating material.
  • the electrolyte composite may be positioned between the negative electrode and the positive electrode.
  • an electronically insulating material may be positioned between the positive electrode and the electrolyte composite.
  • 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 [00110] 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.
  • 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.
  • the electronically insulating material may further comprise a porous support.
  • the porous support may be a glass fiber, porous polymer film, or a separator.
  • 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). [00112] 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 [00113] 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.
  • 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 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).
  • BETI bis(pentafluoroethanesulfonyl)imide
  • TFSI bis(fluorosulfonyl)imide
  • TfO trifluoromethanesulfonate
  • TF trifluoromethanesulfonate
  • 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.
  • 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.
  • 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.
  • PEGMA poly[poly(ethylene glycol) methyl ether acrylate]
  • PEO poly(ethylene oxide)
  • PS poly[4-styrenesulfonyl(triflu
  • ND 24-015 Clause 28.
  • 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.
  • 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( ⁇ -caprolactone)- poly(trimethylene carbonate) (PCL-PTMC), poly(ethylene oxide)-polystyrene (PEO-PS), derivatives thereof, and salts thereof.
  • PCL-PTMC poly(trimethylene carbonate)
  • PEO-PS poly(ethylene oxide)-polystyrene
  • derivatives thereof and salts thereof.
  • Clause 32 The electrolyte composite of any one of clauses 1–31, wherein the matrix is non- covalently associated.
  • the matrix selected from the group consisting of PEO-TFSI, PEO-LiBETI, PCL-PTMC-LiTFSI, PEO-LiPPC6TFSI, PEO-Mg(TFSI) 2 , PEO-NaClO 4 , and PEO-KBF 4 .
  • PEGMA- LiPSTFSI poly[poly(ethylene glycol) methyl ether acrylate]-poly[(4-styrenesulfonyl)(trifluoromethanesulfonyl)imide] lithium salt
  • Clause 36 The electrolyte composite of any one of clauses 1–35, having an ionic conductivity of at least 10 ⁇ 5 S/cm.
  • Clause 37. The electrolyte composite of any one of clauses 1–36, having an electronic conductivity of at least 10 ⁇ 5 S/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.
  • 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 47. The electrochemical cell of any one of clauses 42–46, wherein the electronically insulating material further comprises a porous support.
  • CT complex Tetrathiafulvalene (TTF, 100 mg, 0.49 mmol) and tetracyanoquinodimethane (TCNQ, 100 mg, 0.49 mmol) were each dissolved in 40 mL of anhydrous acetonitrile (CH 3 CN) 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.
  • TTF Tetrathiafulvalene
  • TCNQ tetracyanoquinodimethane
  • TTF-TCNQ charge-transfer
  • 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.
  • CT complex 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.
  • 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.
  • 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 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.
  • LiTFSI lithium bis(trifluoromethylsulfonyl)imide
  • TTF-TCNQ was used as the charge-transfer complex.
  • 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.
  • Composite PEO-NaClO 4 -[TTF-TCNQ] This composite electrolyte was prepared following the general procedure above where PEO was used as the polymer, sodium perchlorate (NaClO 4 , Sigma Aldrich) was used as the ionic species, and TTF-TCNQ was used as the charge- transfer complex.
  • Composite PEO-KBF 4 -[TTF-TCNQ] This composite electrolyte was prepared following the general procedure above where PEO was used as the polymer, potassium tetrafluoroborate (KBF 4 , Sigma Aldrich) was used as the ionic species, and TTF-TCNQ was used as the charge-transfer complex.
  • 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.
  • 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.
  • KSTFSI styrenesulfonyl(trifluoromethyl sulfonyl)imide potassium salt
  • Electrolyte without CT complex [00127] 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 Composites ND 24-015 Exemplary Methods for Measuring Ionic Conductivity [00128] 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.
  • Electrodes were separated by a 100 ⁇ m-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 ⁇ 10 6 Hz 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 [00129] Various types of conduction phenomena were observed in the AC measurement results. In some cases, only ionic conductivity was visible.
  • 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 ⁇ ' 0.1Hz is the maximum value possible for the electronic conductivity for the measured material. In instances where ⁇ ' is decreasing as frequency is decreased towards 0.1 Hz, then the electronic conductivity must be less than the value of ⁇ ' 0.1Hz . ND 24-015 Table 4.
  • DSC Differential Scanning Calorimetry of Exemplary Electrolyte Composites
  • 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 [00134] 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).
  • 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 [00138] 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.
  • 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 ⁇ L ethylene acrylate, 297 ⁇ L poly(ethylene glycol) diacrylate (PEGDA, average Mn 700), and 32 ⁇ L 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.
  • the cellulose-based tri-layer configuration was prepared wherein a cellulose-based porous separator (diameter 10 mm, thickness 20 ⁇ m, 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.
  • the temperature was decreased at 5 °C/min with 5 min of stabilization time ND 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 -7 S/cm.
  • 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. [00141] 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 ⁇ 10 6 Hz 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.
  • 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).

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Abstract

L'invention concerne des composites d'électrolyte non poreux comprenant une pluralité de cristaux de transfert de charge comportant une molécule acceptrice d'électrons et une molécule donneuse d'électrons. Les cristaux de transfert de charge sont dispersés dans une matrice comprenant une espèce ionique et un polymère. L'espèce ionique peut être un cation, un anion ou un polyanion. Le polymère peut être un homopolymère ou un copolymère. L'espèce ionique et le polymère peuvent être liés de manière non covalente ou covalente. L'invention concerne également la mise en oeuvre des composites d'électrolyte dans une cellule électrochimique.
PCT/US2024/057080 2023-11-24 2024-11-22 Composites d'électrolyte non poreux Pending WO2025111549A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6268430B1 (en) * 1998-04-16 2001-07-31 E. I. Du Pont De Nemours And Company Ionomers and ionically conductive compositions
US10483576B2 (en) * 2014-12-04 2019-11-19 Lg Chem, Ltd. Polymer electrolyte membrane
US20210384490A1 (en) * 2018-02-22 2021-12-09 Sumitomo Metal Mining Co., Ltd. Metal composite hydroxide and method for producing same, positive electrode active material for non-aqueous electrolyte secondary battery and method for producing same, and non-aqueous electrolyte secondary battery
US20230018258A1 (en) * 2020-03-18 2023-01-19 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery using same
US20230317920A1 (en) * 2022-03-31 2023-10-05 Idemitsu Kosan Co., Ltd Production method for sulfide solid electrolyte

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6268430B1 (en) * 1998-04-16 2001-07-31 E. I. Du Pont De Nemours And Company Ionomers and ionically conductive compositions
US10483576B2 (en) * 2014-12-04 2019-11-19 Lg Chem, Ltd. Polymer electrolyte membrane
US20210384490A1 (en) * 2018-02-22 2021-12-09 Sumitomo Metal Mining Co., Ltd. Metal composite hydroxide and method for producing same, positive electrode active material for non-aqueous electrolyte secondary battery and method for producing same, and non-aqueous electrolyte secondary battery
US20230018258A1 (en) * 2020-03-18 2023-01-19 Panasonic Intellectual Property Management Co., Ltd. Solid electrolyte material and battery using same
US20230317920A1 (en) * 2022-03-31 2023-10-05 Idemitsu Kosan Co., Ltd Production method for sulfide solid electrolyte

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YANG LINGYU, SCHAEFER JENNIFER L.: "Water-Assisted Ion Conduction in Solid-State Charge-Transfer Complex Electrolytes for Lithium Batteries", ACS ENERGY LETTERS, ACS, AMERICAN CHEMICAL SOCIETY, vol. 8, no. 5, 12 May 2023 (2023-05-12), American Chemical Society, pages 2426 - 2431, XP093318778, ISSN: 2380-8195, DOI: 10.1021/acsenergylett.3c00627 *

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