ENERGY STORAGE APPLICATION ELECTROLYTES AND ELECTRODE COMPOSITIONS COMPRISING POLYACRYLATES OR POLYACRYLAMIDES

CROSS-REFERENCE TO RELATED APPLICATIONS

[001] This application claims the benefit of priority to U.S. Provisional Application No. 63/147,339 filed on February 9, 2021, which is hereby incorporated by reference in its entirety.

TECHNICAL FIELD

[002] The present disclosure relates to polymers and additives that may be used in energy storage applications, and more specifically, in liquid and solid-state electrolytes. The present disclosure further relates to batteries and capacitors containing the electrolytes.

BACKGROUND

[003] Renewable sources of energy (e.g., photovoltaic, eolic, and the like) that do not rely on coal, petroleum products, or natural gas are seeing increased use in a variety of applications based on their substantially reduced environmental impact. As efforts to reduce greenhouse gas emissions become even more critical, their use is expected to increase further. However, even though renewable energy sources are naturally replenishing (i.e., virtually inexhaustible), they are limited in the amount of energy that is available per unit of time. As a result, there is a need to develop new, highly efficient energy storage systems that meet the technological demands of both existing and developing applications. These storage systems should also be safe and non-toxic.

SUMMARY

[004] In one aspect, the present disclosure provides a polymer comprising a unit of Formula (I):

(i) G ¹ and G ² are independently absent or selected from the group consisting of C=0, alkyl, cycloalkyl, aryl, arylalkylene, alkylenearyl, ether, polyether, O and NR ^a , wherein both G ¹ and G ² cannot simultaneously be absent, N, O or C=0;

(ii) R ^a is selected from the group consisting of H and alkyl;

(iii) G ³ is selected from the group consisting of alkylene, cycloalkylene, and alkenylene;

(iv) R ¹ and R ² are independently selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkylenearyl, heteroaryl, and alkyleneheteroaryl;

(v) R ³ is selected from the group consisting of-CN and -NC.

[005] In one aspect, the present disclosure provides a polymer comprising a unit of Formula (II):

(i) G ¹ is selected from the group consisting of -C(0)-0-alkylene-, - C(0)-NR ^a -alkylene-, -C(0)-0-ether-, -C(0)-NR ^a -ether-, -C(O)- O-polyether-, and -C(0)-NR ^a -polyether-;

(ii) G ² is selected from the group consisting of -O-C(O)-, - NR ^a -C(0)-, -0-C(0)-alkylene-, -0-C(0)-alkenylene-, -NR ^a -C(0)-alkylene-, -NR ^a -C(0)-alkenylene-, (iii) R ¹ and R ² are independently selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkylenearyl, heteroaryl, and alkyleneheteroaryl;

(iv) R ^a is selected from the group consisting of H and alkyl; and

(v) Het is a lithium-binding heterocyclic group.

[006] In one aspect, an electrolyte composition is provided comprising a polymer disclosed herein, e.g., a polymer comprising a unit of Formula (I) or a polymer comprising a unit of Formula (II).

[007] In one aspect, the present disclosure provides a battery, comprising: a. an anode; b. a cathode; and c. an electrolyte composition of the present disclosure operatively coupled with the anode and cathode.

[008] In one aspect, the present disclosure provides a capacitor, comprising an electrolyte composition of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

[009] Figure 1A provides the chemical structure of Poly- 1 and a description of certain subunits.

[010] Figure IB provides the chemical structure of Poly-1 Copolymer.

[011] Figure 2 shows the ¾ NMR Spectra of Poly-1 and Poly-1 Copolymer in DMSO-de.

[012] Figure 3 is a graph showing a TGA analysis of Poly- 1 and Poly-1 Copolymer. [013] Figure 4 is a graph showing a DSC analysis of Poly-1 and Poly-1 copolymer (second heating scan at 10 K/min).

[014] Figure 5 is a non-limiting example of a method for processing Poly-1 and Poly-2 solid polymer electrolytes (SPEs).

[015] Figure 6 is a graph showing a TGA analysis of Poly-1 with different LiTFSI concentrations. [016] Figure 7 is a graph showing a DSC analysis of Poly-2 with different LiTFSI concentrations (second heating scan at 10 K/min).

[017] Figure 8 shows an FTIR spectra of Poly- 1 and Poly- 1-25 wt. % LiTFSI.

[018] Figure 9 shows Arrhenius plots of ionic conductivity for Poly-1 -25 wt. % LiTFSI, Poly- 1-35 wt. % LiTFSI, Poly- 1-45 wt. % LiTFSI electrolytes.

[019] Figure 10 shows a non-limiting method of LSV cells assembly.

[020] Figure 11 shows a graph of the electrochemical stability of Poly- 1 -25 wt. % LiTFSI and Poly-1 -45 wt. % LiTFSI electrolytes at 70 °C.

[021] Figure 12 provides the chemical structure of Poly-2.

[022] Figure 13 shows the 'H NMR spectra of Batch 1 and Batch 2 of Poly-2 in CDCb. [023] Figure 14 shows an FUR spectra of Batch 1 and Batch 2 of Poly-2.

[024] Figure 15 is a graph showing a TGA analysis of Poly-2 Batch 1 and Batch 2.

[025] Figure 16 is a graph showing a DSC analysis of Poly-2 Batch 1 and Batch 2 (second heating scan at 10 K/min).

[026] Figure 17 is a graph showing a TGA analysis of Poly-2 with different LiTFSI concentrations.

[027] Figure 18 is a graph showing a DSC analysis of Poly-2 with different LiTFSI concentrations (second heating scan at 10 K/min).

[028] Figure 19A-19D shows Poly-2 structure highlighting the main vibration modes analyzed by FTIR (Figure 19A); FTIR spectra in the wavenumber range of 2000 cm ^-1 to 950 cm ^-1 of Poly-2, LiTFSI, Poly-2-25 wt. % LiTFSI and Poly-2-45 wt. % LiTFSI (Figure 19B); FTIR spectra in the wavenumber range from 950 to 450 cm ^-1 of Poly-2, LiTFSI, Poly-2-25 wt. % LiTFSI and Poly-2-45 wt. % LiTFSI (Figure 19C); and the proposed coordination mechanism between lithium cation and Poly-2 (Figure 19D).

[029] Figure 20 shows the chemical structures of the SPEs of Table 8.

DETAILED DESCRIPTION

[030] Energy storage is a field with a tremendous push for innovation due to the use of renewable sources of energy like photovoltaic and eolic that do not rely on coal, petroleum products or natural gas - fossil fuels that are major greenhouse gases contributors. These increasingly used renewable energy sources need electrical storage systems capable of storing the energy produced in a non-continuous fashion and releasing it when needed. In the energy storage field, rechargeable batteries are of special importance due to the portable devices market. Cost and performance of new advanced batteries are key to extend the usage of new energy sources. Applications such as hybrid and electric cars, smartphones, and wearables need batteries with higher energy and power densities, shorter charge cycles and safer systems. Currently, lithium ion batteries are the most widely used type of battery in those applications thanks to the lightness and high energy density of lithium, which confers important advantages to these type of batteries compared to Pb-acid, Ni-Cd or NiMH ones. Nevertheless, commercially available lithium ion batteries have important limitations such as safety hazards, self-discharge, and environmental toxicity among others. Some causes of these limitations are lithium metal dendrite growth that can cause short circuits and flammable organic solvent usage that can produce toxic compounds and catch fire easily.

[031] In contrast, solid-state batteries offer particular advantages. They do not contain toxic and flammable liquid organic solvents, which translates to increased safety and reduced toxicity. In addition, they have potentially higher energy and power density. The main challenge for solid-state electrolytes is the ionic conductivity since ions move slower in solids than they perform in the liquid-based organic solvents. Ionic movement through the electrolyte is needed to move the electron flow in the external component of the battery. In polymer-based electrolytes, crystallinity and polymer composition determines the pace at which ions move between electrodes.

[032] Poly(ethylene oxide) (PEO) has been considered the gold standard of polymer based solid-state electrolytes due to its intrinsic ionic conductivity at high temperatures and its ability to dissolve lithium salts. However, PEO has low ionic conductivities at room temperature (10 ⁵ S/cm), far from the lithium ion battery ionic conductivities and what is desirable for commercial applications (10 ³ S/cm).

[033] Other compounds that have been tested and found successful for one or multiple property requirements are methacrylates, polyethers, fluoro organic compounds, poly acrylonitrile, polystyrene, polyvinylpyrrolidone (PVP), polypyrrole (PPy), polyacrylic acid, polycyanoacrylates and analogue molecules. Additives such as succinonitrile have also demonstrated ionic conductivity enhancement.

[034] In addition to the material composition, the polymer structure plays an important role in the system performance. Some approaches consist of copolymer electrolytes with one type of material providing structural integrity and another one providing ionic conductivity. Others use additives intercalated in the polymer to enhance the ionic conductivity.

[035] The challenge for solid-state batteries consists of finding a system with properties that fill all the requirements without sacrificing a particular one. Those requirements include: high ionic conductivity (measured in S/cm), high energy and power density (in Wh/kg and W/cm ² ), high stability, high capacity retention (in % of retention after x number of cycles), non-flammability, high thermal stability, good mechanical properties to avoid dendrite formation (shear modulus in Pa), flexibility, being easy to produce and cheap (in $/kWh), and having high voltage (in V).

[036] The present disclosure provides polymers and additives that are useful in energy storage applications, such as in liquid and solid-state electrolytes.

Definitions

[037] Unless context indicates otherwise, the features of the invention can be used in any combination. Any feature or combination of features set forth can be excluded or omitted. Certain features of the invention, which are described in separate embodiments may also be provided in combination in a single embodiment. Features of the invention, which are described in a single embodiment may also be provided separately or in any suitable sub combination. All combinations of the embodiments are disclosed herein as if each and every combination were individually disclosed. All sub-combinations of the embodiments and elements are disclosed herein as if every such sub-combination were individually disclosed.

[038] Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The detailed description is divided into sections only for the reader’s convenience and disclosure found in any section may be combined with that in another section. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the exemplary methods and materials are now described. All publications mentioned herein are incorporated by reference to disclose and describe the methods and/or materials in connection with which the publications are cited. Reference to a publication is not an admission that the publication is prior art.

[039] The singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise.

[040] The conjunction “and/or” means both “and” and “or,” and lists joined by “and/or” encompasses all possible combinations of one or more of the listed items.

[041] The term “about” and its grammatical equivalents in relation to a reference numerical value and its grammatical equivalents as used herein can include a range of values plus or minus 10% from that value, such as a range of values plus or minus 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% from that value. For example, the amount “about 10” includes amounts from 9 to 11.

[042] “Alkyl” or “alkyl group” refers to a fully saturated, straight or branched hydrocarbon chain having from one to twelve carbon atoms, and which is attached to the rest of the molecule by a single bond. Alkyls comprising any number of carbon atoms from 1 to 12 are included. An alkyl comprising up to 12 carbon atoms is a C1-C12 alkyl, an alkyl comprising up to 10 carbon atoms is a C1-C10 alkyl, an alkyl comprising up to 6 carbon atoms is a C1-C6 alkyl and an alkyl comprising up to 5 carbon atoms is a C1-C5 alkyl. A C1-C5 alkyl includes C5 alkyls, C4 alkyls, C3 alkyls, Ci alkyls and Ci alkyl i.e., methyl). A C1-C6 alkyl includes all moieties described above for C1-C5 alkyls but also includes Ce alkyls. A C1-C10 alkyl includes all moieties described above for C1-C5 alkyls and C1-C6 alkyls, but also includes C7, Cs, C9 and C10 alkyls. Similarly, a C1-C12 alkyl includes all the foregoing moieties, but also includes C11 and C12 alkyls. Non-limiting examples of C1-C12 alkyl include methyl, ethyl, «-propyl, /-propyl, «-butyl, /-butyl, sec-butyl, /-butyl, «-pentyl, t- amyl, «-hexyl, «-heptyl, «-octyl, 2-ethylhexyl, «-nonyl, «-decyl, «-undecyl, and «- dodecyl. Unless stated otherwise specifically in the specification, an alkyl group can be optionally substituted.

[043] “Alkylene” or “alkylene chain” refers to a fully saturated, straight or branched divalent hydrocarbon chain radical, and having from one to twelve carbon atoms. Non- limiting examples of C1-C12 alkylene include methylene, ethylene, propylene, «-butylene, and the like. The alkylene chain is attached to the rest of the molecule through a single bond and to a radical group (e.g., those described herein) through a single bond. The points of attachment of the alkylene chain to the rest of the molecule and to the radical group can be through one carbon or any two carbons within the chain. Unless stated otherwise specifically in the specification, an alkylene chain can be optionally substituted.

[044] “Alkenyl” or “alkenyl group” refers to a straight or branched hydrocarbon chain having from two to twelve carbon atoms, and having one or more carbon-carbon double bonds. Each alkenyl group is attached to the rest of the molecule by a single bond. Alkenyl group comprising any number of carbon atoms from 2 to 12 are included. An alkenyl group comprising up to 12 carbon atoms is a C2-C12 alkenyl, an alkenyl comprising up to 10 carbon atoms is a C2-C10 alkenyl, an alkenyl group comprising up to 6 carbon atoms is a C2-C6 alkenyl and an alkenyl comprising up to 5 carbon atoms is a C2-C5 alkenyl. A C2-C5 alkenyl includes C5 alkenyls, C4 alkenyls, C3 alkenyls, and C2 alkenyls. A C2-C6 alkenyl includes all moieties described above for C2-C5 alkenyls but also includes Ce alkenyls. A C2-C10 alkenyl includes all moieties described above for C2-C5 alkenyls and C2-C6 alkenyls, but also includes C7, Cx, C9 and C10 alkenyls. Similarly, a C2-C12 alkenyl includes all the foregoing moieties, but also includes C11 and C12 alkenyls. Non-limiting examples of C2- C12 alkenyl include ethenyl (vinyl), 1-propenyl, 2-propenyl (allyl), iso-propenyl, 2-methyl- 1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4- pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-heptenyl, 2-heptenyl, 3-heptenyl, 4-heptenyl, 5-heptenyl, 6-heptenyl, 1-octenyl, 2-octenyl, 3-octenyl, 4-octenyl,

5-octenyl, 6-octenyl, 7-octenyl, 1-nonenyl, 2-nonenyl, 3-nonenyl, 4-nonenyl, 5-nonenyl,

6-nonenyl, 7-nonenyl, 8-nonenyl, 1-decenyl, 2-decenyl, 3-decenyl, 4-decenyl, 5-decenyl, 6-decenyl, 7-decenyl, 8-decenyl, 9-decenyl, 1-undecenyl, 2-undecenyl, 3-undecenyl, 4- undecenyl, 5-undecenyl, 6-undecenyl, 7-undecenyl, 8-undecenyl, 9-undecenyl, 10- undecenyl, 1-dodecenyl, 2-dodecenyl, 3-dodecenyl, 4-dodecenyl, 5-dodecenyl, 6- dodecenyl, 7-dodecenyl, 8-dodecenyl, 9-dodecenyl, 10-dodecenyl, and 11-dodecenyl. Unless stated otherwise specifically in the specification, an alkyl group can be optionally substituted.

[045] “Aryl” refers to a hydrocarbon ring system comprising hydrogen, six to eighteen carbon atoms and at least one aromatic ring, and which is attached to the rest of the molecule by a single bond. For purposes of this disclosure, the aryl can be a monocyclic, bicyclic, tricyclic or tetracyclic ring system, which can include fused or bridged ring systems. Aryls include, but are not limited to, aryls derived from aceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene, benzene, chrysene, fluoranthene, fluorene, as-indacene, .s-indacene, indane, indene, naphthalene, phenalene, phenanthrene, pleiadene, pyrene, and triphenylene. Unless stated otherwise specifically in the specification, the “aryl” can be optionally substituted.

[046] “Arylene” refers to a divalent aromatic radical, which is attached to the rest of the molecule through a single bond and to a radical group (e.g., those described herein) through a single bond. The points of attachment of the arylene to the rest of the molecule and to the radical group can be through any two carbons of the aromatic ring. Unless stated otherwise specifically in the specification, an arylene can be optionally substituted.

[047] “Carbocyclyl,” “carbocyclic ring” or “carbocycle” refers to a rings structure, wherein the atoms which form the ring are each carbon, and which is attached to the rest of the molecule by a single bond. Carbocyclic rings can comprise from 3 to 20 carbon atoms in the ring. Carbocyclic rings include aryls and cycloalkyl, cycloalkenyl, and cycloalkynyl as defined herein. Unless stated otherwise specifically in the specification, a carbocyclyl group can be optionally substituted.

[048] “Cycloalkyl” refers to a stable non-aromatic monocyclic or polycyclic fully saturated hydrocarbon consisting solely of carbon and hydrogen atoms, which can include fused or bridged ring systems, having from three to twenty carbon atoms (e.g., having from three to ten carbon atoms) and which is attached to the rest of the molecule by a single bond. Monocyclic cycloalkyls include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Polycyclic cycloalkyls include, for example, adamantyl, norbornyl, decalinyl, 7,7-dimethyl-bicyclo[2.2. l]heptanyl, and the like. Unless otherwise stated specifically in the specification, a cycloalkyl group can be optionally substituted.

[049] “Cycloalkylene” refers to a stable non-aromatic monocyclic or polycyclic fully saturated divalent hydrocarbon consisting solely of carbon and hydrogen atoms, which can include fused or bridged ring systems, having from three to twenty carbon atoms (e.g., having from three to ten carbon atoms). Monocyclic cycloalkylenes include, for example, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, and cyclooctylene. Polycyclic cycloalkylenes include, for example, adamantylene, norbornylene, decalinylene, 7,7-dimethyl-bicyclo[2.2.1]heptanylene, and the like. The cycloalkylene is attached to the rest of the molecule through a single bond and to a radical group (e.g., those described herein) through a single bond. The points of attachment of the cycloalkylene to the rest of the molecule and to the radical group can be through one carbon or any two carbons of the ring. Unless otherwise stated specifically in the specification, a cycloalkyl group can be optionally substituted.

[050] “Cycloalkenyl” refers to a stable non-aromatic monocyclic or polycyclic hydrocarbon consisting solely of carbon and hydrogen atoms, having one or more carbon- carbon double bonds, which can include fused or bridged ring systems, having from three to twenty carbon atoms, preferably having from three to ten carbon atoms, and which is attached to the rest of the molecule by a single bond. Monocyclic cycloalkenyls include, for example, cyclopentenyl, cyclohexenyl, cycloheptenyl, cycloctenyl, and the like. Polycyclic cycloalkenyls include, for example, bicyclo[2.2.1]hept-2-enyl and the like. Unless otherwise stated specifically in the specification, a cycloalkenyl group can be optionally substituted.

[051] “Heterocyclyl,” “heterocyclic ring” or “heterocycle” refers to a stable saturated, unsaturated, or aromatic 3- to 20-membered ring which consists of two to nineteen carbon atoms and from one to six heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, and which is attached to the rest of the molecule by a single bond. Heterocyclyl or heterocyclic rings include heteroaryls, heterocyclylalkyls, heterocyclylalkenyls, and hetercyclylalkynyls. Unless stated otherwise specifically in the specification, the heterocyclyl can be a monocyclic, bicyclic, tricyclic or tetracyclic ring system, which can include fused or bridged ring systems; and the nitrogen, carbon or sulfur atoms in the heterocyclyl can be optionally oxidized; the nitrogen atom can be optionally quaternized; and the heterocyclyl can be partially or fully saturated. Examples of such heterocyclyl include, but are not limited to, dioxolanyl, thienyl[l,3]dithianyl, decahydroisoquinolyl, imidazolinyl, imidazolidinyl, isothiazolidinyl, isoxazolidinyl, morpholinyl, octahydroindolyl, octahydroisoindolyl, 2-oxopiperazinyl, 2-oxopiperidinyl, 2-oxopyrrolidinyl, oxazolidinyl, piperidinyl, piperazinyl, 4-piperidonyl, pyrrolidinyl, pyrazolidinyl, quinuclidinyl, thiazolidinyl, tetrahydrofuryl, trithianyl, tetrahydropyranyl, thiomorpholinyl, thiamorpholinyl, 1 -oxo-thiomorpholinyl, and 1 , 1 -dioxo-thiomorpholinyl. Unless stated otherwise specifically in the specification, a heterocyclyl group can be optionally substituted.

[052] “Heteroaryl” refers to a 5- to 20-membered ring system comprising hydrogen atoms, one to nineteen carbon atoms, one to six heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur, at least one aromatic ring, and which is attached to the rest of the molecule by a single bond. For purposes of this disclosure, the heteroaryl can be a monocyclic, bicyclic, tricyclic or tetracyclic ring system, which can include fused or bridged ring systems; and the nitrogen, carbon or sulfur atoms in the heteroaryl can be optionally oxidized; the nitrogen atom can be optionally quaternized. Examples include, but are not limited to, azepinyl, acridinyl, benzimidazolyl, benzothiazolyl, benzindolyl, benzodioxolyl, benzofuranyl, benzooxazolyl, benzothiazolyl, benzothiadiazolyl, benzo [/?][! ,4]dioxepinyl, 1 ,4-benzodioxanyl, benzonaphthofuranyl, benzoxazolyl, benzodioxolyl, benzodioxinyl, benzopyranyl, benzopyranonyl, benzofuranyl, benzofuranonyl, benzothienyl (benzothiophenyl), benzotriazolyl, benzo[4,6]imidazo[l,2-a]pyridinyl, carbazolyl, cinnolinyl, dibenzofuranyl, dibenzothiophenyl, furanyl, furanonyl, isothiazolyl, imidazolyl, indazolyl, indolyl, indazolyl, isoindolyl, indobnyl, isoindolinyl, isoquinolyl, indolizinyl, isoxazolyl, naphthyridinyl, oxadiazolyl, 2-oxoazepinyl, oxazolyl, oxiranyl, 1-oxidopyridinyl, 1-oxidopyrimidinyl, 1 -oxidopyrazinyl, 1 -oxidopyridazinyl, 1 -phenyl- 1 //-pyrrolyl, phenazinyl, phenothiazinyl, phenoxazinyl, phthalazinyl, pteridinyl, purinyl, pyrrolyl, pyrazolyl, pyridinyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinazolinyl, quinoxalinyl, quinolinyl, quinuclidinyl, isoquinolinyl, tetrahydroquinolinyl, thiazolyl, thiadiazolyl, triazolyl, tetrazolyl, triazinyl, and thiophenyl (i.e. thienyl). Unless stated otherwise specifically in the specification, a heteroaryl group can be optionally substituted.

[053] “Alkylenearyl” refers to a radical of the formula -Ri-Rj, wherein Ri is an alkylene and Rj is an aryl, each of which is as defined herein. Unless stated otherwise specifically in this specification, an alkylenearyl group can be optionally substituted.

[054] “Alkyleneheteroaryl” refers to a radical of the formula -Ri-Rj, wherein Ri is an alkylene and Rj is a heteroaryl, each of which is as defined herein. Unless stated otherwise specifically in this specification, an alkyleneheteroaryl group can be optionally substituted.

[055] “Arylalkylene” refers to a radical of the formula -Ri-Rj-, wherein Ri is an aryl and Rj is alkylene, each of which is as defined herein. Unless stated otherwise specifically in the specification, an arylalkylene group can be optionally substituted.

[056] “Ether” refers to a radical of the formula -Ri-O-Rj-, wherein Ri and Rj are each independently an alkylene, alkenylene, alkynylene, cycloalkyl, aryl, or the like. An ether of the present disclosure can be acyclic or cyclic. In some embodiments, the ether is a repeating unit of an oligomer or polymer referred to herein as a poly ether, e.g., polyethylene glycol. Unless stated otherwise specifically in the specification, an ether or polyether can be optionally substituted.

[057] As used herein, the term “substituted” means any of the groups described herein (e.g., alkyl, alkenyl, alkynyl, alkoxy, aryl, aralkyl, carbocyclyl, cycloalkyl, cycloalkenyl, cycloalkynyl, haloalkyl, heterocyclyl, and/or heteroaryl) wherein at least one hydrogen atom is replaced by a bond to a non-hydrogen atoms such as, but not limited to: a halogen atom such as F, Cl, Br, and I; an oxygen atom in groups such as hydroxyl groups, alkoxy groups, and ester groups; a sulfur atom in groups such as thiol groups, thioalkyl groups, sulfone groups, sulfonyl groups, and sulfoxide groups; a nitrogen atom in groups such as amines, amides, alkylamines, dialkylamines, arylamines, alkylarylamines, diarylamines, N-oxides, imides, and enamines; a silicon atom in groups such as trialkylsilyl groups, dialkylarylsilyl groups, alkyldiarylsilyl groups, and triarylsilyl groups; and other heteroatoms in various other groups. “Substituted” also means any of the above groups in which one or more hydrogen atoms are replaced by a higher-order bond (e.g., a double- or triple-bond) to a heteroatom such as oxygen in oxo, carbonyl, carboxyl, and ester groups; and nitrogen in groups such as imines, oximes, hydrazones, and nitriles. For example, “substituted” includes any of the above groups in which one or more hydrogen atoms are replaced with -NRgRh, -NRgC(=0)Rh, -NRgC(=0)NRgRh, -NRgC(=0)0Rh, -NRgSC Rh, - 0C(=0)NRgRh, -ORg, -SRg, -SORg, -SC Rg, -OSC Rg, -SC ORg, =NS0 ₂ Rg, and -SC NRgRh. “Substituted” also means any of the above groups in which one or more hydrogen atoms are replaced with -C(=0)R _g , -C(=0)0Rg, -C(=0)NRgRh, -CH ₂ S0 ₂ Rg, -CFFSC NRgRh. In the foregoing, R _g and Rh are the same or different and independently hydrogen, alkyl, alkenyl, alkynyl, alkoxy, alkylamino, thioalkyl, aryl, aralkyl, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloalkylalkyl, haloalkyl, haloalkenyl, haloalkynyl, heterocyclyl, N- heterocyclyl, heterocyclylalkyl, heteroaryl, /V-heteroaryl and/or heteroarylalkyl. “Substituted” further means any of the above groups in which one or more hydrogen atoms are replaced by a bond to an amino, cyano, hydroxyl, imino, nitro, oxo, thioxo, halo, alkyl, alkenyl, alkynyl, alkoxy, alkylamino, thioalkyl, aryl, aralkyl, cycloalkyl, cycloalkenyl, cycloalkynyl, cycloalkylalkyl, haloalkyl, haloalkenyl, haloalkynyl, heterocyclyl, N- heterocyclyl, heterocyclylalkyl, heteroaryl, //-heteroaryl and/or heteroarylalkyl group. In addition, each of the foregoing substituents can also be optionally substituted with one or more of the above substituents.

Polymers of the Present Disclosure:

[058] In one aspect, the present disclosure provides polymers comprising a unit of Formula (I) or Formula (II) and electrolyte compositions comprising such polymers. The compounds of Formula (I) and (II) can be additives that when added to an electrolyte composition improve the electrolyte’s performance characteristics (such as, enhancing conductivity and/or reducing crystallinity). Polymers comprising a unit of Formula (I) or a unit of Formula (II) may be added to any appropriate electrolyte composition known to those skilled in the art.

[059] In some embodiments, the present disclosure provides a polymer comprising a unit of Formula (I):

( ⁱ ) G ¹ and G ² are independently absent or selected from the group consisting of C=0, alkylene, cycloalkylene, arylene, arylalkylene, alkylenearyl, ether, polyether, O and NR ^a , wherein both G ¹ and G ² cannot simultaneously be absent, N, O or C=0;

(ii) R ^a is selected from the group consisting of H and alkyl;

(iii) G ³ is selected from the group consisting of alkylene, cycloalkyl, and alkenylene;

(iv) R ¹ and R ² are independently selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkylenearyl, heteroaryl, and alkyleneheteroaryl;

(v) R ³ is selected from the group consisting of-CN and -NC.

[060] In some embodiments of Formula (I), R ¹ and R ² are H. In some embodiments, R ¹ is H and R ² is alkyl. In some embodiments, alkyl is selected from the group consisting of methyl, ethyl, propyl, or butyl. In some embodiments, alkyl is methyl.

[061] In some embodiments of Formula (I), G ¹ is C=0, arylene, or absent. In some embodiments, G ¹ is C=0. In some embodiments, G ¹ is arylene. In some embodiments, aryl is phenyl. In some embodiments, G ¹ is absent. [062] In some embodiments of Formula (I), G ² is selected from the group consisting of O, NR ^a , alkylene, ether, and polyether. In some embodiments, G ² is selected from the group consisting of alkylene, ether, and polyether. In some embodiments, G ² is alkylene. In some embodiments, alkylene is Ci-6alkylene. In some embodiments, G ² is an ether. In some embodiments, the ether is an alkyl ether. In other embodiments, the ether is an aryl ether. In some embodiments, the aryl ether is a phenyl ether. In some embodiments, G ² is a polyether. In some embodiments, In some embodiments, the polyether is -O- (alkylene)-O-. In some embodiments, when G ² is -0-(alkylene)-0-, the alkylene is a C2-5alkylene. In some embodiments, the polyether is -0-(CH2CH2)-0- In some embodiments, G ² is O or NR ^a . In some embodiments, G ² is O. In some embodiments, G ² is NR ^a .

[063] In some embodiments of Formula (I), G ¹ is C=0 and G ² is O. In some embodiments, G ¹ is C=0 and G ² is NR ^a . In some embodiments, G ¹ is absent and G ² is O. In some embodiments of Formula (I), G ¹ is C=0 and G ² is poly ether. In some embodiments, the polyether is -0-(alkylene)-0- In some embodiments, alkylene is C2-5alkylene. In some embodiments, alkylene is ethylene. In some embodiments, alkylene is propylene. In some embodiments, G ² is polyethylene glycol. In some embodiments, the

4-OCH ₂ CH ₂ -L polyethylene glycol is represented by ' , wherein n is the number of repeating units. In some embodiments, n is an integer from 1 to 10, including about 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10 including all ranges and values therebetween. In some embodiments, n is an integer from 1 to 8. In some embodiments, n is an integer from 1 to 6. In some embodiments, n is an integer from 1 to 4. In some embodiments, n is 1 or 2. In some embodiments, n is 1. In some embodiments, n is 2. In some embodiments, n is 3. In some embodiments, n is 4.

[064] In some embodiments, G ¹ is absent and G ² is NR ^a . In some embodiments, R ^a is alkyl. In some embodiments, R ^a is methyl, ethyl, or isopropyl. In some embodiments, R ^a is methyl. In some embodiments, R ^a is H.

[065] In some embodiments of Formula (I), G ¹ is aryl and G ² is selected from the group consisting of alkylene, ether, and polyether. In some embodiments, G ¹ is arylene and G ² is polyether. In some embodiments, aryl is phenyl. In some embodiments, the polyether is -0-(alkylene)-0- In some embodiments, alkylene is Cv alkylene. In some embodiments, alkylene is ethylene. In some embodiments, alkylene is propylene. In some

OH embodiments, the alkylene is propylene-2-ol, i.e.,

[066] In some embodiments of Formula (I), the -G ³ -R ³ is in the para position. In some embodiments, the -G ³ -R ³ is in the meta position. In some embodiments, G ³ is alkylene (e.g., Ci-salkylene) and R ³ is -CN. In some embodiments, G ³ is -(CIL·)- (i.e., methylene) and R ³ is -CN. In some embodiments, G ³ is alkenylene (e.g., Ci-salkenylene) and R ³ is - NC. In some embodiments, G ³ is -(CHCH)- (i.e., ethylene) and R ³ is -NC. Without being bound by any particular theory, sidechains comprising -CN or -NC can solvate a cation (e.g., a Li cation), which promotes salt dissociation in a SPE.

[067] In some embodiments, the present disclosure provides a polymer comprising a unit of Formula (la):

[068] In some embodiments, the present disclosure provides a polymer comprising a unit of Formula (lb): (lb), wherein a is an integer from 1-4; and R ¹ , R ² , G ³ , and n are as defined above for Formula (I).

[069] In some embodiments of Formula (lb), a is an integer from 1-3. In some embodiments, a is 1 or 2. In some embodiments, a is 1. In some embodiments, a is 2.

[070] In some embodiments of Formula (lb), n is an integer from 1-10, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, including any range therebetween. In some embodiments n is an integer from 1-4. In some embodiments, n is 1. In some embodiments, n is 4.

[071] In some embodiments, the present disclosure provides a polymer comprising a unit of Formula (I) selected from the group consisting of:

[072] In some embodiments, the polymer comprises the unit In some embodiments, the polymer comprises the unit , wherein n is an integer from 1 to 8, e.g., 1, 2, 3, 4, 5, 6, 7, 8, including any range therebetween. In some embodiments, the polymer comprises the unit In some embodiments, the polymer comprises the unit [073] In some embodiments, the present disclosure provides a polymer comprising a unit of Formula (I) selected from the group consisting of:

[075] In some embodiments, the polymer of the present disclosure is amorphous. Without being bound by any particular theory, amorphous polymers are believed to provide flexibility of the material at micro-scale (segmental mobility) that enhances ion mobility. It is generally understood that lithium ions are large enough to need space for them to move.

[076] In some embodiments, the glass transition temperature of the polymers of the present disclosure is less than about -65 °C, less than about -60 °C, less than about -55 °C, less than about -50 °C, or less than about -45 °C. In some embodiments, the glass transition temperature of the polymers of the present disclosure is less than about -55 °C.

[077] In some embodiments, the polymer of the present disclosure comprises chemically crosslinked units. In some embodiments, the units are crosslinked by a methylene bridge. , wherein

(i) G ¹ is selected from the group consisting of -C(0)-0-alkylene- - C(0)-NR ^a -alkylene- -C(0)-0-ether- -C(0)-NR ^a -ether- -C(O)- O-polyether- and -C(0)-NR ^a -polyether-;

(ii) G ² is selected from the group consisting of-O-C(O)-, - NR ^a -C(0)-, -0-C(0)-alkylene- -0-C(0)-alkenylene- -NR ^a -C(0)-alkylene-, -NR ^a -C(0)-alkenylene-,

(iii) R ¹ and R ² are independently selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkylenearyl, heteroaryl, and alkyleneheteroaryl;

(iv) R ^a is selected from the group consisting of H and alkyl; and

(v) Het is a lithium-binding heterocyclic group.

[079] In some embodiments of Formula (II), R ¹ and R ² are H. In some embodiments, R ¹ is H and R ² is alkyl. In some embodiments, alkyl is selected from the group consisting of methyl, ethyl, propyl, or butyl. In some embodiments, alkyl is methyl.

[080] In some embodiments of Formula (II), G ¹ is -C(0)-0-alkylene-. In some embodiments, the alkylene is a Ci-6alkylene. In some embodiments, the alkylene is ethylene, propylene, or butylene. In some embodiments, the alkylene is ethylene. [081] In some embodiments of Formula (II), G ² is -O-C(O)- or -0-C(0)-alkenylene- In some embodiments, G ² is -O-C(O)-. In some embodiments, G ² is -O-C(O)- alkenylene-. In some embodiments, the alkenylene is C2-6alkenylene. In some embodiments, the alkenylene is ethenylene.

[082] In some embodiments of Formula (II), G ¹ is -C(0)-0-alkylene- and G ² is -O- C(O)-. In some embodiments, the alkylene is a Ci-6alkylene. In some embodiments, the alkylene is ethylene, propylene, or butylene. In some embodiments, the alkylene is ethylene.

[083] In some embodiments of Formula (II), G ¹ is -C(0)-0-alkylene- and G ² is -O- C(0)-alkenylene-. In some embodiments, the alkylene is a Ci-6alkylene. In some embodiments, the alkylene is ethylene. In some embodiments, the alkenylene is C2-6alkenylene. In some embodiments, the alkenylene is ethenylene.

[084] As indicated above, Formula (II) comprises a Het moiety, which represents any heterocyclic group capable of binding lithium. The lithium-binding groups of the present disclosure can be chelating groups, and include a Lewis basic heteroatom, e.g., nitrogen or oxygen, that can form a coordinate (i.e., dative) bond to a Lewis acidic Li ion by donating a lone pair of electrons. In some embodiments, a lithium ion is bound by one or more Het groups to form a Li-heteroatom complex.

[085] The Het moiety of Formula (II) can be any lithium-binding group known in the art. In some embodiments of Formula (II), Het is selected from the group consisting of 2- pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, quinolinyl, isoquinolinyl, N-alkyl-indol-3-yl, N-alkyl-imidazol-4-yl, and N-alkyl-imidazol-5-yl. In some embodiments, Het is selected from the group consisting of 2-pyridyl, 3-pyridyl, 4- pyridyl, N-alkyl-indol-3-yl, N-alkyl-imidazol-4-yl, and N-alkyl-imidazol-5-yl. In some embodiments, alkyl is methyl, ethyl, or isopropyl. In some embodiments, alkyl is methyl

[086] In some embodiments, the present disclosure provides a polymer comprising a unit of Formula (Ha): wherein R ¹ , R ² , G ¹ , and G ² are as defined above for Formula

(II)

[087] In some embodiments, the polymer comprises the unit . In some embodiments, the polymer comprises the unit

[088] In some embodiments, the polymers of the present disclosure are amorphous.

[089] In some embodiments, the glass transition temperature of the polymers of the present disclosure is less than about -65 °C, less than about -60 °C, less than about -55 °C, less than about -50 °C, or less than about -45 °C. In some embodiments, the glass transition temperature of the polymers of the present disclosure is less than about -55 °C.

[090] In some embodiments, the polymers of the present are stable from about -20 °C to about 100 °C, e.g., about -20 °C, about -15 °C, about -10 °C, about -5 °C, about 0 °C, about 5 °C, about 10 °C, about 15 °C, about 20 °C, about 25 °C, about 30 °C, about 35 °C, about 40 °C, about 45 °C, about 50 °C, about 55 °C, about 60 °C, about 65 °C, about 70 °C, about 75 °C, about 80 °C, about 85 °C, about 90 °C, about 95 °C, or about 100 °C, including all ranges and values therebetween.

[091] In some embodiments, the polymer of the present disclosure comprises chemically crosslinked units. In some embodiments, the units are crosslinked by a methylene bridge.

Homopolymers of the Present Disclosure:

[093] In some embodiments, the present disclosure provides a homopolymer, wherein the homopolymer comprises a unit of Formula (I): wherein G ¹ , G ² , G ³ , R ¹ , R ² , and R ³ are as defined above. [094] As understood by one of skill in the art, the homopolymers of the present disclosure comprise identical repeating monomeric units provided by the units of Formula (I), above. For example, a homopolymer comprising units of Formula (I) may be represented by the following formula: wherein Ai is a monomeric unit of Formula (I), and wherein r is an integer from 3 to

10,000.

[096] In some embodiments, the present disclosure provides a homopolymer comprising identical units of Formula (la): wherein G ² , G ³ , R ¹ , and R ² are as defined above for Formula

(I)·

[097] In some embodiments, the present disclosure provides a homopolymer comprising identical units of Formula (I) or Formula (la), wherein the unit of Formula (I) or Formula

(Ia) is: , wherein n is an integer from 1 to 8, e.g., 1, 2, 3, 4, 5, 6, 7, 8, including any range therebetween. In some embodiments, the present disclosure provides a homopolymer comprising identical units of Formula (I) or Formula (la), wherein the unit of Formula (I) or Formula (la) is:

F , comprises identical units of Formula (I) or Formula (la), wherein the unit of Formula (I) or Formula (la) is:

[098] In some embodiments, the present disclosure provides a homopolymer comprising identical units of Formula (I), wherein the unit of Formula (I) is selected from the group consisting of:

[099] In some embodiments, the present disclosure provides a homopolymer comprising identical units of Formula (II): wherein G ¹ , G ² , R ¹ , R ² , and Het are as defined above.

[100] As understood by one of skill in the art, the homopolymers of the present disclosure comprise a polymer comprising identical repeating monomeric units provided by the compounds of Formula (II), above. For example, a homopolymer comprising units of Formula (I) may be represented by the following formula: wherein Ai is a monomeric unit of Formula (II), and wherein r is an integer from 3 to

10,000. [101] In some embodiments, the present disclosure provides a homopolymer comprising identical units of Formula (Ha):

[102] In some embodiments, the present disclosure provides a homopolymer comprising identical units of Formula (II), wherein the unit of Formula (II) is selected from the group consisting of:

[103] In some embodiments, the homopolymers of the present disclosure are characterized by a uniform dispersity (£ ⁾ ). In some embodiments, the homopolymers are characterized by a non-uniform dispersity. In some embodiments, the homopolymers are characterized by a D from about 1 to about 20, e.g., about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, about 18, about 19, or about 20.

[104] In some embodiments, the homopolymer is solid polymer electrolyte (SPE). In some embodiments, the homopolymer is a liquid polymer electrolyte.

Heteropolymers of the Present Disclosure:

[105] In one aspect, the present disclosure provides heteropolymers comprising units of Formula (I), heteropolymers comprising units of Formula (II), or mixtures thereof. The heteropolymers of the present disclosure may be used as an electrolyte composition or added to any appropriate electrolyte composition known in the art. Heteropolymers comprising any order of polymer units of Formula (I), Formula (II), or mixtures thereof may be prepared by polymerizing an appropriate monomer according to any polymerization method that is known to those skilled in the art. Such methods include, but are not limited to addition (chain-reaction) polymerization and condensation (step- reaction) polymerization. In some embodiments, the polymerization is cationic polymerization. In some embodiments, the polymerization is anionic polymerization. In some embodiments, the polymerization is radical polymerization.

[106] In some embodiments, the heteropolymers comprise two or more different units of Formula (I), i.e., two or more units of Formula (I), wherein at least one of the definitions of the groups G ¹ , G ² , G ³ , R ¹ , R ² , and R ³ are not the same. In some embodiments, monomers are polymerized to form a heteropolymer of the present disclosure.

[107] In some embodiments, the present disclosure provides a heteropolymer comprising two or more units of Formula (I): wherein G ¹ , G ² , G ³ , R ¹ , and R ² are as defined above.

[108] As understood by one of skill in the art, a heteropolymer of the present disclosure comprises a polymer comprising two or more non-identical units of Formula (I), above. For example, the heteropolymer may be represented by formulas including, but not limited to: wherein Ai, Ai, and A3 are different monomer units of Formula (I), and wherein s is an integer from 3 to 100,000. In some embodiments, s is an integer from 1,000 to 100,000. In some embodiments, s is an integer from 5,000 to 100,000. wherein G ² , G ³ , R ¹ , and R ² are as defined above for Formula

(I)·

[110] In some embodiments, the present disclosure provides a heteropolymer comprising one or more units of Formula (I) selected from the group consisting of:

[111] In some embodiments, the present disclosure provides a heteropolymer comprising one or more units of Formula (I) selected from the group consisting of: [112] In some embodiments, the heteropolymer comprises the unit:

[113] In some embodiments, the heteropolymers comprise two or more different units of Formula (II), i.e., two or more units of Formula (II), wherein at least one of the definitions of the groups G ¹ , G ² , G ³ , R ¹ , R ² , and Het are not the same. In some embodiments, monomers are polymerized to form a heteropolymer of the present disclosure.

[114] In some embodiments, the present disclosure provides a heteropolymer comprising two or more units of Formula (II):

[115] As understood by one of skill in the art, a heteropolymer of the present disclosure comprises a polymer comprising two or more non-identical units of Formula (II), above. For example, the heteropolymer may be represented by formulas including, but not limited to: wherein at least two of Ai, Ai, and A3 are different monomer units of Formula (II), and wherein s is an integer from 3 to 100,000. In some embodiments, s is an integer from 1,000 to 100,000. In some embodiments, s is an integer from 5,000 to 100,000. [116] In some embodiments, the present disclosure provides a heteropolymer, wherein the heteropolymer comprises two or more units of Formula (Ha):

[117] In some embodiments, the present disclosure provides a heteropolymer comprising one or more units of Formula (II) selected from the group consisting of:

[118] In some embodiments, the heteropolymers comprising units of Formula (I) are cross-linked polymers comprising two or more homopolymers, for example: wherein Ai is a monomer of Formula (I), A2 is a second monomer of Formula (I) distinct from Ai, and n and n are each independently an integer in the range of 3 to 2,000,000. In some embodiments, n and n are each independently an integer in the range of 10,000 to 2,000,000. In some embodiments, n and n are each independently an integer in the range of 50,000 to 2,000,000. In some embodiments, n and n are each independently an integer in the range of 100,000 to 2,000,000.

, wherein Ai is a monomer of Formula (II), A2 is a second monomer of Formula (II) distinct from Ai, and n and n are each independently an integer in the range of 3 to 2,000,000. In some embodiments, n and n are each independently an integer in the range of 10,000 to 2,000,000. In some embodiments, n and n are each independently an integer in the range of 50,000 to 2,000,000. In some embodiments, n and n are each independently an integer in the range of 100,000 to 2,000,000.

[120] In some embodiments, one or more monomeric units of Formula (I) is incorporated into a polymer according to any method known in the art, including those disclosed herein, with one or more monomeric units of Formula (II) to form a heteropolymer of the present disclosure. The monomers can be polymerized in any order, including but not limited to: , wherein at least two of Ai, A2, and A3 are different monomer units of Formula (I) or Formula (II), and wherein s is an integer from 3 to 100,000. In some embodiments, s is an integer from 1,000 to 100,000. In some embodiments, s is an integer from 5,000 to 100,000.

[121] In some embodiments, the heteropolymer of the present disclosure is a copolymer. In some embodiments, the copolymer is a block copolymer. In some embodiments, the heteropolymer comprises two or more units selected from the group consisting of:

[122] In some embodiments, one or more monomeric units of Formula (I), Formula (II), or mixtures thereof (e.g., any of those disclosed herein) are incorporated into a polymer by a method known in the art with one or more additional monomers (i.e., monomer units not encompassed by the Formulas (I) and (II)) to form a heteropolymer of the present disclosure. In some embodiments, the additional monomer comprises ethylene oxide (EO). In some embodiments, the additional monomer is PAN. In some embodiments, a synergetic effect results between the one or more monomeric units of Formula (I), Formula (II), or mixtures thereof and the one or more additional PAN monomers, where — CºN groups can create chelates with transition metal ions diminishing the dissolution of Mn/Ni ions from the cathode, while — C=0 groups can significantly decrease the formation of lithium dendrites by a favorable interaction with Li ions. In some embodiments, the one or more additional monomers promotes ionic conductivity, while the one or more monomeric units disclosed herein contributes to salt dissociation and mechanical stiffness.

[123] In some embodiments, the heteropolymers in the electrolyte composition have a uniform dispersity (£ ⁾ ). In another embodiment, the heteropolymers in the electrolyte composition have a non-uniform dispersity. In some embodiments, D is from about 1 to about 20, e.g., about 1, about 2, about 3, about 4, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, about 18, about 19, or about 20.

[124] In some embodiments, the heteropolymer electrolyte is a solid polymer electrolyte (SPE). In some embodiments, the heteropolymer electrolyte is a liquid polymer electrolyte. Electrolyte Compositions of the Present Disclosure

[125] In some embodiments, the present disclosure provides electrolyte compositions comprising the polymers described herein. In some embodiments, the disclosed polymers are conductive polymers. In some embodiments, the electrolyte compositions are solid polymer electrolyte compositions.

[126] In some embodiments, the electrolyte composition further comprises a polymer selected from the group consisting of polyethylene oxide (PEO), poly(vinyl chloride) (PVC), poly(vinyl alcohol) (PVA), poly(vinylpyrrolidone) (PVP, poly(acrylic acid) (PAA), poly(acrylonitrile) (PAN), poly(vinylidene fluoride) (PVdF), poly(ethylmethacrylate) (PEMA), poly(methylmethacrylate) (PMMA), poly(vinylidenefluoride-hexafluoro propylene) (PVdF-HFP), poly ( -caprolactone) (PCL), and chitosan. In a certain embodiments, the one or more additional polymers is selected from the group consisting of PAN and PEO.

[127] In some embodiments, the electrolyte composition further comprises an organic fluoropolymer. In some embodiments, the fluoropolymer is selected from the group consisting of poly(vinylidene fluoride) (PVdF) and poly(vinylidene fluoride-hexafluoro propylene) (PVdF-HFP). In a specific embodiment, the fluoropolymer is poly(vinylidene fluoride) (PVdF).

[128] In some embodiments, the electrolyte composition further comprises a polymer selected from the group consisting of poly(ethylene oxide), a polyether, polyacrylonitrile, polystyrene, polyvinyl pyrrolidone, polypyrrole, polyacrylic acid, polyphenylene sulfide, polyether ether ketone, polyamines, polyimides, polyamides, and polycyanoacrylates.

[129] In some embodiments, the electrolyte composition further comprises a compound selected from the group consisting of poly(ethylene oxide), methacrylate, a polyether, a fluoro organic compound, polyacrylonitrile, polystyrene, polyvinyl pyrrolidone, polypyrrole, polyacrylic acid, polyphenylene sulfide, polyether ether ketone, vinyl pyridine, polyamines, polyimides, polyamides and polycyanoacrylates. [130] In some embodiments, the present disclosure provides electrolyte compositions comprising the additives and polymers of the present disclosure. Electrolyte compositions, as they are known in the art, can be prepared and designed by techniques that include, but are not limited to blending, cross-linking polymer matrices, comb-branched copolymers, doping of nanomaterials, adding binary salt systems, incorporation of additives (e.g., plasticizers), impregnation with ionic liquids, and reinforcement with inorganic fillers and/or conductivity enhancers.

[131] In some embodiments, the electrolyte compositions of the present disclosure are prepared by cross-linking. In some embodiments the electrolyte compositions of the present disclosure are prepared by cross-linking a homopolymer and/or heteropolymer of the present disclosure with a polymer selected from the group consisting of poly(ethylene oxide), a polyether, polyacrylonitrile, polystyrene, polyvinyl pyrrolidone, polypyrrole, polyacrylic acid, polyphenylene sulfide, polyether ether ketone, polyamines, polyimides, polyamides, and poly cyanoacrylates. In some embodiments, the electrolyte compositions of the present disclosure are prepared by cross-linking a homopolymer and/or heteropolymer of the present disclosure with a polymer selected from the group consisting of polyethylene oxide (PEO), poly(vinyl chloride) (PVC), poly(vinyl alcohol) (PVA), poly(vinylpyrrolidone) (PVP, poly(acrylic acid) (PAA), poly(acrylonitrile) (PAN), poly(vinylidene fluoride) (PVdF), poly(ethylmethacrylate) (PEMA), poly(methyl methacrylate) (PMMA), poly(vinylidenefluoride-hexafluoro propylene) (PVdF-HFP), poly ( -caprolactone) (PCL), and chitosan. In some embodiments, the electrolyte composition is prepared by cross-linking a homopolymer and/or heteropolymer of the present disclosure with PEO or PAN. In some embodiments, the electrolyte composition is prepared by cross-linking a homopolymer and/or heteropolymer of the present disclosure with a polyacrylate or derivative thereof, e.g., a polymer prepared from methyl acrylate, ethyl acrylate, butyl acrylate, methacrylate, butyl methacrylate, hydroxyethyl methacrylate, acrylonitrile, and the like. In some embodiments, the cross-linked polymers of the present disclosure exhibit high ionic conductivity (> 10 ⁴ S/cm) and good mechanical strength (e.g., shear modulus >10 ⁹ Pa). In some embodiments, good mechanical strength provides resistance to dendrite growth and/or avoids short-circuits between positive and negative electrodes. In certain embodiments, the improved properties are due to the amorphous nature (i.e., low crystallinity) of the CPE.

[132] In some embodiments, the present disclosure provides electrolyte compositions prepared by blending. Polymer blending is a process of mixing at least two polymers that have no chemical bonding between them. In some embodiments, blending, as disclosed herein, provides electrolyte materials that have superior properties compared to the individual components alone, for example improved physical properties (e.g., mechanical stability) and electrical properties (e.g., conductivity). In some embodiments, a blended electrolyte composition has higher conductivity due to a lower amount of crystallinity. Decreasing the amount of crystallinity can result in the interactions between the polymers of the composite electrolyte being maximized.

[133] In some embodiments, the electrolyte compositions of the present disclosure are prepared by blending a polymer of the present disclosure with a polymer selected from the group consisting of polyethylene oxide (PEO), poly(vinyl chloride) (PVC), poly(vinyl alcohol) (PVA), poly(vinylpyrrolidone) (PVP, poly(acrylic acid) (PAA), poly(acrylonitrile) (PAN), poly(vinylidene fluoride) (PVdF), poly(ethylmethacrylate) (PEMA), poly(methyl methacrylate) (PMMA), poly(vinylidenefluoride-hexafluoro propylene) (PVdF-HFP), poly ( -caprolactone) (PCL), and chitosan. In some embodiments, the polymer of the present disclosure in blended with polypropylene carbonate (PPC), PVdF, PAN or PEO. In some embodiments, a composite polymer electrolyte of the present disclosure is prepared by blending a homopolymer and/or heteropolymer of the present disclosure with PAN or PEO. Without being bound by any particular theory, the polymer of the present disclosure may confer mechanical, thermal, and/or electrochemical stability, while the additional polymer may promote ionic conductivity suitable for high voltage and other applications.

[134] The properties (e.g., ionic conductivity, crystallinity, mechanical stability, thermal stability, etc.) of the electrolyte composition of the present disclosure can be tuned by adjusting the ratio of the homopolymer or heteropolymer to the additional polymer. In some embodiments, the ratio of homopolymer or heteropolymer to the additional polymer is about 10:1, about 9:1, about 8:1, about 7:1, about 6:1, about 5:1, about 4:1, about 3:1, about 2:1, about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, or about 1:10, including all ratios and values therebetween. In some embodiments, the ratio is about 1:1. In some embodiments, the ratio is about 2:1. In some embodiments, the ratio is about 1 :2.

[135] In some embodiments, the electrolyte compositions of the present disclosure comprise a solid polymer electrolyte (SPE). In another embodiment, the electrolyte composition is a liquid polymer electrolyte.

[136] In some embodiments, the electrolyte compositions of the present disclosure further comprise one of more alkali metal salts. In some embodiments, the alkali metal salt is a lithium salt or a sodium salt. In some embodiments, the alkali metal salt is a lithium salt. In some embodiments, the lithium salt is selected from the group consisting LiPF6, LiN(CF3S02)2 (FiTFSI), FiCICF, F1CF3SO3, and F12B4O7, or combinations thereof. In some embodiments, the lithium salt is FiTFSI. In some embodiments, the salt is a non- metal salt. In some embodiments, the non-metal salt is an ammonium salt. In some embodiments, the ammonium salt is of CH3COONH4. In some embodiments, a CPE doped with a salt exhibits better electrical stability and conductivity. In some embodiments, the electrolyte compositions of the present disclosure are blended with any of the one or more alkali metal salts. In some embodiments, the electrolyte compositions of the present disclosure are blended with a non-metal salt.

[137] In some embodiments, the electrolyte compositions of the present disclosure further comprise one or more fillers or conductivity enhancers. In some embodiments, the conductivity enhancer or filler is selected from the group consisting of succinonitrile, AI2O3, AIOOH, BaTiC , BN, F1N3, F1AIO2, lithium fluorohectorite, and fluoromica clay. In some embodiments, the filler or conductivity enhancer is selected from the group consisting of silicon oxide (S1O2), magnesium oxide (MgO), aluminum oxide (AI2O3), titanium oxide (T1O2), zirconium oxide (ZrCh), nanoclays, and talc, or combinations thereof. In some embodiments, the nanoclay is selected from the group consisting of montmorillonite (MMT), kaolinite, and saponite. In some embodiments, the filler is hydrophobic-fumed silica. In some embodiments, the filler is a zeolite. In some embodiments, the filler is a nanomaterial. In some embodiments, the fillers are small, electrochemically inert particles. In some embodiments, doping of fillers into CPEs improves ionic conductivity, mechanical stability, thermal stability, reduces crystallinity and the glass transition temperature, stabilizes the highly conductive amorphous phase, and provides superior interfacial stability in contact with various electrode materials. In some embodiments, the fillers used in the present compositions reduce the crystallinity of polymers, hinder them from recrystallization or increase the degree of amorphicity, which leads to better ionic conductivity of the polymer. In some embodiments, the filler or conductivity enhancer in the electrolyte composition is present in an amount of from about 5 to about 10% by weight, e.g., about 5%, about 6%, about 7%, about 8%, about 9%, or about 10%, including all ranges and values therebetween.

[138] In some embodiments, the electrolyte compositions of the present disclosure further comprise one or more plasticizers. In some embodiments, the plasticizer is selected from the group consisting of dimethyl carbonate (DMC), dioctyl adipate (DOA), dibutyl phthalate (DBP), diethyl carbonate (DEC), propylene carbonate (PC), ethylene carbonate (EC), glycol sulfite (GS), methylethylcarbonate (MEC), and butyrolactone (BL). In some embodiments, the plasticizer is selected from the group consisting of ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), propylene carbonate (PC), N,N dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetraglyme (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), propylene carbonate (PC), g- butyrolactone (BL) and ionic liquids (e.g. pyrrolidinium-based IL). In some embodiments, plasticizers dissolve more charge carriers to increase the mobile medium for ions. In some embodiments, the incorporation of plasticizers provide higher ionic conductivity and good thermal and mechanical stabilities.

[139] In some embodiments, the electrolyte compositions of the present disclosure further comprise a compound selected from the group consisting of poly(ethylene oxide), methacrylate, a polyether, a fluoro organic compound, polyacrylonitrile, polystyrene, polyvinyl pyrrolidone, polypyrrole, polyacrylic acid, polyphenylene sulfide, polyether ether ketone, vinyl pyridine, polyamines, polyimides, polyamides, and poly cyanoacrylates. [140] In some embodiments, the electrolyte compositions of the present disclosure further comprise a polymer selected from the group consisting of polypropylene, poly (2,6- dimethyl- 1 ,4-phenylene oxide) (PXE), polyolefins, poly(cyclohexyl methacrylate), poly(cyclohexyl vinyl ether), poly(t-butyl vinyl ether), polyethylene, polynitriles, polysiloxanes, polyphosphazenes, polydiene, a poly ether, polyphenylene sulfide, poly ether ether ketone, polyamines, polyimides, and polyamides.

[141] In some embodiments of the present disclosure, the electrolyte compositions further comprise an electrode stabilizing agent.

Characteristics of Electrolyte Compositions of the Present Disclosure:

[142] The electrolyte compositions of the present disclosure relate to improving and/or enhancing the size, charge rate, thermal stability (e.g., Td,s), mechanical stability, ionic conductivity, power, energy density, and/or life span of the disclosed electrolyte compositions compared to existing technologies.

[143] In some embodiments, the electrolyte compositions of the present disclosure are characterized by an ionic conductivity from about 10 ⁶ to about 10 ² S/cm, e.g., about 10 ⁶ S/cm, about 10 ⁵ S/cm, about 10 ⁴ S/cm, about 10 ³ S/cm, or about 10 ² S/cm, including all ranges and values therebetween. In some embodiments, the ionic conductivity is from about 10 ⁵ to about 10 ³ S/cm. In some embodiments, the ionic conductivity is from about 10 ⁴ to about 10 ³ S/cm. In some embodiments, the ionic conductivity is greater than 10 ⁴ S/cm. In some embodiments, the ionic conductivity is greater than 10 ³ S/cm. In some embodiments, the electrolyte compositions are characterized by an ionic conductivity of 3.0xl0 ⁴ to 3.0xl0 ³ S/cm. In some embodiments, the ionic conductivity is measured at room temperature.

[144] In some embodiments, the electrolyte compositions of the present disclosure are characterized by an electrochemical stability window of from about 1 to about 6 volts against Li/Li ⁺ , e.g., about 1 volt, about 2 volts, about 3 volts, about 4 volts, about 5 volts, or about 6 volts against Li/Li ⁺ , including all ranges and values therebetween. [145] In some embodiments, the electrolyte compositions of the present disclosure do not ignite under the ASTM D4206 test conditions.

[146] In some embodiments, the electrolyte compositions of the present disclosure are stable at a temperature of about 30 °C to about 200 °C, e.g., about 30 °C, about 35 °C, about 40 °C, about 45 °C, about 50 °C, about 55 °C, about 60 °C, about 65 °C, about 70 °C, about 75 °C, about 80 °C, about 85 °C, about 90 °C, about 95 °C, about 100 °C, about 105 °C, about 110 °C, about 115 °C, about 120 °C, about 125 °C, about 130 °C, about 135 °C, about 140 °C, about 145 °C, about 150 °C, about 155 °C, about 160 °C, about 165 °C, about 170 °C, about 175 °C, about 180 °C, about 185 °C, about 190 °C, about 195 °C, or about 200 °C, including all ranges and values therebetween. In some embodiments, the electrolyte composition is stable from about 30 °C to about 100 °C. In some embodiments, the electrolyte composition is stable at a temperature of about 75 °C to about 200 °C. In some embodiments, the electrolyte composition is stable at a temperature of about 100 °C to about 200 °C. In some embodiments, the electrolyte composition is stable at a temperature of about 125 °C to about 200 °C. In some embodiments, the electrolyte composition is stable at a temperature of about 150 °C to about 200 °C. In some embodiments, the electrolyte composition is stable at a temperature of about 175 °C to about 200 °C. In some embodiments, the electrolyte composition is stable at a temperature above 150 °C. In some embodiments, the electrolyte composition is stable from about - 40 °C to about 170 °C.

[147] In some embodiments of the present disclosure, the polymer of the electrolyte composition is characterized by an elastic modulus of at least 1 10 ⁷ Pa, at least 5 10 ⁷ Pa, at least lxlO ⁸ Pa, at least 5xl0 ⁸ Pa, at least lxl0 ⁹ Pa, or at least 5xl0 ⁹ Pa. In some embodiments, the elastic modulus of the polymer is measured by the ASTM D638 test. In some embodiments, the ASTM D638 test is the ASTM D636-14 test.

[148] In some embodiments of the present disclosure, the polymer of the electrolyte composition is characterized by a shear modulus of at least 1 xlO ⁹ Pa, at least 5xl0 ⁹ Pa, at least lxlO ⁸ Pa, at least 5xl0 ⁸ Pa, at least lxlO ⁷ Pa, or at least l xlO ⁷ Pa. In a specific embodiment, the electrolyte composition is characterized by a shear modulus of at least lxlO ⁹ Pa.

[149] In some embodiments of the present disclosure, the electrolyte composition is characterized by a glass transition of less than about -55 °C, less than about -50 °C, less than about -45 °C, less than about -40 °C, less than about -35 °C, or less than about -30 °C. In a specific embodiment, the glass transition temperature is less than about -55 °C. In some embodiments, the glass transition temperature is between about - 55 °C and about -45 °C, e.g., about -55 °C, about -54 °C, about -53 °C, about -52 °C, about -51 °C, about -50 °C, about -49 °C, about -48 °C, about -47 °C, about -46 °C, or about -45°C, including all ranges and values therebetween.

Energy Storage Devices

[150] In some embodiments, the present disclosure provides a battery, comprising: a. an anode; b. a cathode; and c. an electrolyte composition of the present disclosure operatively coupled with the anode and cathode.

[151] In some embodiments, the anode is a lithium metal anode or a carbon anode.

[152] In some embodiments, the cathode is an oxide cathode. In some embodiments, the oxide cathode is selected from the group consisting of LiNiCoMnC (NMC), LiFePC C (LFP), LiNiCoAlC (NCA), LiMmCL (LMO), LiNiO.5Mnl .504 (LNMO), and LiCoCh (LCO). In another embodiment, the cathode is a V2O5 cathode.

[153] In some embodiments, the battery is characterized by a specific energy density of at least 290 Wh/kg, at least 300 Wh/kg, at least 320 Wh/kg, at least 340 Wh/kg, at least 380 Wh/kg, at least 400 Wh/kg. In another embodiment, the battery has a specific energy density in the range of about 295 Wh/kg to about 400 Wh/kg. In still another embodiment, the battery has a specific energy density in the range of about 320 Wh/kg to about 400 Wh/kg. In yet another embodiment, the battery has a specific energy density in the range of about 360 Wh/kg to about 400 Wh/kg. In some embodiments, the battery has a specific energy density of about 700 Wh/kg.

[154] In some embodiments, the battery is characterized by a specific energy of about 100 Wh/kg to about 750 Wh/kg, e.g., about 100 Wh/kg, about 125 Wh/kg, about 150 Wh/kg, about 175 Wh/kg, about 200 Wh/kg, about 225 Wh/kg, about 250 Wh/kg, about 275 Wh/kg, about 300 Wh/kg, about 325 about 350 Wh/kg, about 375 Wh/kg, about 400 Wh/kg, about 425 Wh/kg, about 450 Wh/kg, about 475 Wh/kg, about 500 Wh/kg, about 525 Wh/kg, about 550 Wh/kg, about 575 Wh/kg, about 600 Wh/kg, about 625 Wh/kg, about 650 Wh/kg, about 675 Wh/kg, about 700 Wh/kg, about 725 Wh/kg, or about 750 Wh/kg, including all ranges and values therebetween. In some embodiments, the electrolyte composition is characterized by a specific energy of about 320 Wh/kg to about 700 Wh/kg.

[155] In some embodiments, the battery is characterized by a is characterized by an energy density of about 200 Wh/L to about 1200 Wh/L, e.g., about 200 Wh/L, about 250 Wh/L, about 300 Wh/L, about 350 Wh/L, about 400 Wh/L, about 450 about 500 Wh/L, about 550 Wh/L, about 600 Wh/L, about 650 Wh/L, about 700 Wh/L, about 750 Wh/L, about 800 Wh/L, about 850 Wh/L, about 900 Wh/L, about 950 Wh/L, about 1000 Wh/L, about 1050 Wh/L, about 1100 Wh/L, about 1150 Wh/L, or about 1200 Wh/L, including all ranges and values therebetween. In some embodiments, the electrolyte composition is characterized by an energy density of about 700 Wh/L to about 1100 Wh/L.

[156] In some embodiments, the battery is characterized by a is characterized by capacity of about 0.1 mAh to about 5 mAh, e.g., about 0.1 mAh, about 0.5 mAh, about 1 mAh, about 1.5 mAh, about 2 mAh, about 2.5 mAh, about 3 mAh, about 3.5 mAh, about 4 mAh, about 4.5 mAh, or about 5 mAh, including all ranges and values therebetween. In some embodiments, the capacity of the electrolyte composition is greater than about 1 Ah, greater than about 2 Ah, greater than about 3 Ah, greater than about 4 Ah, or greater than about 5 Ah, including all ranges and values therebetween.

[157] In some embodiments of the present disclosure, the battery is characterized by a Pmax of lkW to about 20 kW, e.g., about 1 kW, about 2 kW, about 3 kW, about 4 kW, about 5 kW, about 6 kW, about 7 kW, about 8 kW, about 9 kW, about 10 kW, about 11 kW, about 12 kW, about 13 kW, about 14 kW, about 15 kW, about 16 kW, about 17 kW, about 18 kW, about 19 kW, or about 20 kW, including all ranges and values therebetween. In some embodiments, the Pmax is at least 8 kW. In some embodiments, the Pmax is greater than 8 kW.

[158] In some embodiments of the present disclosure, the electrolyte composition is characterized by an electrochemical window (EW) in the range of about 3 V to about 6 V, e.g., about 3 V, about 3.2 V, about 3.4 V, about 3.6 V, about 3.8 V, about 4 V, about 4.2 V, about 4.4 V, about 4.6 V, about 4.8 V, about 5 V, about 5.2 V, about 5.4 V, about 5.6 V, about 5.8 V, or about 6 V, including all ranges and values therebetween. In some embodiments, the electrochemical window of the electrolyte composition ranges from about 3 V to about 5 V. In some embodiments, the electrochemical window of the electrolyte composition ranges from about 4 V to about 6 V.

[159] In some embodiments, the battery is a rechargeable battery.

[160] In some embodiments, the battery has a high capacity retention as exhibited by an 85% of retention after 100 number of cycles, an 85% of retention after 500 number of cycles, an 85% of retention after 800 number of cycles, or an 85% of retention after 1000 number of cycles. In another embodiment, the battery has a high capacity retention as exhibited by a 90% of retention after 100 number of cycles, a 90% of retention after 500 number of cycles, a 90% of retention after 800 number of cycles, or a 90% of retention after 1000 number of cycles.

[161] In some embodiments of the present disclosure, the battery is a solid-state battery.

[162] In some embodiments, the present disclosure provides a capacitor, comprising an electrolyte composition of the present disclosure. In some embodiments, the capacitor is a supercapacitor. In some embodiments, the supercapacitor is a double-layer capacitor, a pseudocapacitor, or a hybrid capacitor (i.e., a combination of double- layer and pseudocapacitors) . Applications of the Disclosed Polymers

[163] In some embodiments, the polymers of the present disclosure are suitable for use in high voltage lithium batteries. For such applications, small organic molecules can be introduced to plasticize the polymers disclosed herein (e.g., Poly-1 and Poly-2) in order to promote ionic conductivity for room temperature applications. Without being bound by any particular theory, plasticizers can interact with the polymer chains lowering the Tg and significantly increasing the ambient temperature ionic conductivity. As disclosed herein, this electrolyte configuration is known as gel polymer electrolyte (GPE). In some embodiments, the plasticizers for GPE applications include ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), propylene carbonate (PC), N,N dimethylformamide (DMF), dimethyl sulfoxide (DMSO), tetraglyme (TEGDME), poly(ethylene glycol) dimethyl ether (PEGDME), propylene carbonate (PC), g- butyrolactone (BL) and ionic liquids (e.g. pyrrolidinium-based IL). In some embodiments, the plasticizer is EO-based, carbonate-based, or nitrile-based. In some embodiments, a GPE comprising a polymer of the present disclosure and a plasticizer has a shear modulus > 7 GPa. In some embodiments, a suitable GPa is about 8 to 25 GPa, about 10 to 20 GPa, about 12 to 18 GPa, or about 15 to 25 GPa, including any range or value therebetween.

[164] In some embodiments, the polymers of the present disclosure are suitable for forming electrolytes for high energy density technology. Without being bound by any particular theory, the polymers disclosed herein can have an oxidation potential above 3.8 V (vs Li ⁺ /Li), which is useful for such application. Accordingly, in some embodiments, the polymers of the present disclosure having an oxidation potential above 3.8 V are integrated in high energy technology as scaffolds to reinforce the mechanical/electrochemical properties of another polymer that would work as conducting matrix for the Li+, as GPE by introduction of a suitable plasticizer, or as binder material for high voltage cathode. In some embodiments, the polymers of the present disclosure, e.g., Poly-1 and Poly-2, are copolymerized or blended with different polymers and plasticizers disclosed herein to optimize their use in high energy density applications. In some embodiments, the polymers disclosed herein are jellified to optimize their use as electrolytes in high voltage applications. [165] In some embodiments, the properties observed during the evaluation of the disclosed polymers, e.g., Poly-1 and Poly-2, make them suitable for use within battery technology as: 1) matrices for gel polymer electrolytes (GPEs); 2) electrolytes for high energy density technology; and/or 3) bilayers (polymer binder + polymer separator or double-layer electrolyte where two different polymers face two different interfaces).

[167] Thus, a double-layer electrolyte comprising Poly-1 or Poly-2 as an SPE layer in contact with the cathode side, and a more conducting EO-based polymer in the anode side is considered a potential architecture for integration between a high voltage cathode and a LiM anode. The ionic conductivity delivered by Poly-1 and Poly-2 electrolytes should be further improved before their use as catholyte. This could be achieved by different strategies by blending with additives/plasticizers stable to high voltage such PC, SCN, and/or GTN or by slight modifications of the polymer architecture to reach a more flexible polymer chain.

FURTHER EMBODIMENTS OF THE DISCLOSURE

[168] Other subject matter contemplated by the present disclosure is set out in the following numbered embodiments.

1. A polymer comprising a unit of Formula (I): , wherein i. G ¹ and G ² are independently absent or selected from the group consisting of C=0, alkylene, cycloalkyl, aryl, arylalkylene, alkylenearyl, ether, polyether, O and NR ^a , wherein both G ¹ and G ² cannot simultaneously be absent, N, O or C=0; ii. R ^a is selected from the group consisting of H and alkyl; iii. G ³ is selected from the group consisting of alkylene, cycloalkyl, and alkenylene; iv. R ¹ and R ² are independently selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkylenearyl, heteroaryl, and alky leneheteroary 1 ; v. R ³ is selected from the group consisting of-CN and -NC.

2. The polymer of embodiment 1 , wherein R ¹ and R ² are H.

3. The polymer of embodiment 1, wherein R ¹ is H and R ² is alkyl.

4. The polymer of embodiment 1 , wherein the -G ³ -R ³ is in the para position.

5. The polymer of embodiment 1, wherein the -G ³ -R ³ is in the meta position.

6. The polymer of any one of embodiments 1-5, wherein G ² is selected from the group consisting of alkylene, ether, and polyether.

7. The polymer of any one of embodiments 1-5, wherein G ¹ is C=0 and G ² is O.

8. The polymer of any one of embodiments 1-5, wherein G ¹ is C=0 and G ² is NR ^a .

9. The polymer of any one of embodiments 1-5, wherein G ¹ is absent and G ² is O or

NR ^a .

10. The polymer of any one of embodiments 1-5, wherein G ¹ is aryl and G ² is selected from the group consisting of alkylene, ether, and polyether.

11. The polymer of any one of embodiments 1-10, wherein G ³ is alkylene and R ³ is - CN.

12. The polymer of any one of embodiments 1-10, wherein G ³ is -(CH2)- and R ³ is - CN. 13. The polymer of any one of embodiments 1-10, wherein G ³ is alkenylene and R ³ is

-NC.

14. The polymer of any one of embodiments 1-10, wherein G ³ is -(CHCH)- and R ³ is

-NC.

14a. The polymer of any one of embodiments 1-10, wherein G ³ is -(CFL·)- and R ³ is -

NC.

15. The polymer of any one of embodiments 1-3 and 6-10, wherein the unit of Formula (I) is:

15a. The polymer of embodiment 15, wherein G ² is -0-(CH2CH20) _n -, wherein n is an integer from 1 -6.

15b. The polymer of embodiment 15a, wherein n is i.

15c. The polymer of embodiment 15a, wherein n is 4.

15d. The polymer of any one of embodiments 15-15c, wherein G ³ is alkylene.

15e. The polymer of any one of embodiments, 15-15d, wherein G ³ is -(CH2)-.

16. The polymer of embodiment 1 , wherein the polymer comprising the unit of Formula (I) is selected from the group consisting of:

17. The polymer of embodiment 1 , wherein the polymer comprises the unit:

18a. The polymer of embodiment 1, wherein the polymer comprises the unit:

19. The polymer of embodiment 1, wherein the polymer comprises a unit selected from the group consisting of:

21. The polymer of any one of embodiments 1-20, wherein the polymer comprises chemically crosslinked units.

22. The polymer of embodiment 20, wherein the units are crosslinked by a methylene bridge.

23. A polymer comprising a unit of Formula (II):

Het wherein i. G ¹ is selected from the group consisting of -C(0)-0-alkylene-, - C(0)-NR ^a -alkylene-, -C(0)-0-ether- -C(0)-NR ^a -ether-, - C(0)-0-polyether- and -C(0)-NR ^a -polyether-; iii. R ¹ and R ² are independently selected from the group consisting of H, alkyl, cycloalkyl, aryl, alkylenearyl, heteroaryl, and alkyleneheteroaryl; iv. R ^a is selected from the group consisting of H and alkyl; and v. Het is a lithium-binding heterocyclic group.

25. The polymer of embodiment 23, wherein R ¹ is H and R ² is alkyl. 26. The polymer of any one of embodiments 23-25, wherein Het is selected from the group consisting of 2-pyridyl, 3-pyridyl, 4-pyridyl, N-alkyl-indol-3-yl, N-alkyl- imidazol-4-yl, and N-alkyl-imidazol-5-yl.

26a. The polymer of any one of embodiments 23-26, wherein Het is 2-pyridyl.

27. The polymer of any one of embodiments 23-26, wherein G ¹ is -C(0)-0- alkylene- and G ² is -O-C(O)-.

28. The polymer of any one of embodiments 23-26, wherein G ¹ is -C(0)-0- alkylene- and G ² is -0-C(0)-alkenylene-.

28a. The polymer of embodiment 27 or 28, wherein the alkylene is a C2-ioalkylene. 28b. The polymer of embodiment 27 or 28, wherein the alkylene is a C2-6alkylene.

29. The polymer of any one of embodiments 23-28, wherein unit of Formula (II) is: bodiment 23, wherein the polymer comprises the unit:

31. The polymer of embodiment 23, wherein the polymer comprises the unit:

32. The polymer of any one of embodiments 1-31, wherein the polymer is amorphous.

33. The polymer of any one of embodiments 1-32, wherein the glass transition temperature of the polymer is less than about -55°C.

34. An electrolyte composition comprising the polymer of any one of embodiments 1- 32.

35. The electrolyte composition of embodiment 34, further comprising a compound selected from the group consisting of poly(ethylene oxide), methacrylate, a polyether, a fluoro organic compound, polyacrylonitrile, polystyrene, polyvinyl pyrrolidone, polypyrrole, polyacrylic acid, polyphenylene sulfide, polyether ether ketone, vinyl pyridine, polyamines, polyimides, polyamides and polycyanoacrylates.

36. The electrolyte composition of any one of embodiments 34-35, further comprising an alkali metal salt.

37a. The electrolyte composition of embodiment 36 or 37, wherein the alkali metal salt is LiTFSI.

38. The electrolyte composition of any one of embodiments 34-37, further comprising an electrode stabilizing agent. 39. The electrolyte composition of any one of embodiments 34-38, further comprising a conductivity enhancer or filler.

40. The electrolyte composition of embodiment 39, wherein the conductivity enhancer or filler is selected from the group consisting of succinonitrile, AI2O3, AIOOH, BaTiC , BN, L1N3, L1AIO2, lithium fluorohectorite, and fluoromica clay.

41. The electrolyte composition of any one of embodiments 34-40, wherein the composition is a solid.

42. The electrolyte composition of any one of embodiments 34-41, wherein the electrolyte composition has an ionic conductivity of 3.0xl0 ⁴ to 3.0xl0 ³ (S/cm).

43. The electrolyte composition of any one of embodiments 34-42, wherein the electrolyte composition has an electrochemical stability window of from about 1 to about 6 volts against Li/Li ⁺ .

44. The electrolyte composition of any one of embodiments 34-43, wherein the electrolyte composition does not ignite under the ASTM D4206 test conditions.

45. The electrolyte composition of any one of embodiments 34-44, wherein the electrolyte composition is stable at a temperature of about 30°C to about 200°C.

46. The electrolyte composition of any one of embodiments 34-45, wherein electrolyte composition is characterized by an elastic modulus of at least 1 / 10 ⁷ Pa, at least 5 x 10 ⁷ Pa, at least 1 ^c 10 ⁸ Pa, at least 5 ^c 10 ⁸ Pa, at least 1 ^c 10 ⁹ Pa, or at least 5xl0 ⁹ Pa.

47. A battery, comprising: a. an anode; b. a cathode; and c. an electrolyte composition of any one of embodiments 34-46 operatively coupled with the anode and cathode.

48. The battery of embodiment 47, wherein the battery has a specific energy density of at least 290 Wh/kg, at least 300 Wh/kg, at least 320 Wh/kg, at least 340 Wh/kg, at least 380 Wh/kg, at least 400 Wh/kg. 49. The battery of any one of embodiments 47-48, wherein the battery has a specific energy density of about 700 Wh/kg.

50. The battery of any one of embodiments 47-49, wherein the battery is a rechargeable battery.

51. The battery of any of embodiments 47-50, wherein the battery has a high capacity retention as exhibited by an 85% of retention after 100 number of cycles, an 85% of retention after 500 number of cycles, an 85% of retention after 800 number of cycles, or an 85% of retention after 1000 number of cycles.

52. A capacitor, comprising an electrolyte composition of any of embodiments 34-46.

53. The capacitor of embodiment 52, wherein the capacitor is a supercapacitor.

EXAMPLES

[169] General Methods

[170] The polymers of the present disclosure, e.g., Poly-1 (Figure 1 A), Poly-1 Copolymer (Figure IB), and Poly-2 (Figure 12), may be prepared according to any method known in the art, such as those described in Vivaldo-Lima, E., Saldivar- Guerra, E. (2013). Handbook of Polymer Synthesis, Characterization, and Processing. Germany: Wiley, which is incorporated herein by reference in its entirety.

[171] Nuclear magnetic resonance spectroscopy [NMR, Bruker 300 Ultrashield (300 MHz for 1H)] was used to characterize the structure and purity degree of Poly- 1. Chemical shifts (d) are reported in ppm relative to residual solvent signals [chloroform (CDCF), and dimethyl sulfoxide (CD ₃ SOCD ₃ )].

[172] Thermogravimetric analysis (TGA) was performed on a NETZSCH thermo microbalance TG 209 FI Libra® under Ar flow from 30 to 600 °C at a heating rate of 10 °C min ^-1 in order to determine the decomposition onset of both polymers and SPEs.

[173] The phase transitions of the polymers and SPEs were analyzed on a differential scanning calorimeter (DSC, Q2000, TA instruments). The samples were sealed under Ar in aluminum pans. For the analysis two consecutive scans at a cooling/heating rate of 10 °C min ¹ from -80 to 200 °C were carried out. [174] The ionic conductivity of developed SPEs was determined by electrochemical impedance spectroscopy (EIS) measurements on a VMP3 potentiostat (Biologic) in a frequency range from 10 ¹ to 106 Hz with a voltage amplitude of 100-500 mV. CR2032 type coin cells using two stainless steel (SS) blocking electrodes (SS | SPEs | SS) were assembled in an Ar filled glovebox. The diameter of the polymer membrane varies from 4 to 16 mm, this being delimited in the coin cell by a Kapton O-ring. The conductivities were measured in a temperature range from 25 to 100 °C using a Binder KB23 cooling incubator and allowing the cells to reach the thermal equilibrium for at least 1 h before each measurement.

[175] Linear sweep voltammetry (LSV) was used to determine the anodic stability of the polymer electrolytes. The measurement was carried out with a VMP3 potentiostat (Biologic) in a two-electrode cell using stainless steel as working electrode and LiO disk as both counter and reference electrode at 70 °C. The LSV measurements were performed between the open circuit voltage (OCV) and 6.5 V vs. Li+/Li0 at a scan rate of 1 mV s-1. The procedure for the assembly of the coin cell used for this measurement is described in Figure B.

[176] Example 1. Characterization of Poly-1 and Poly-1 Copolymer

[177] Sample preparation: Poly-1 (polydispersity = 1.5) (Figure 1A) and Poly-1 Copolymer (polydispersity = 4.4) (Figure IB) were dried under vacuum at 70 °C to remove residual solvent. Prior to drying, Poly-1 was a compact, amber-colored powder that was sticky and hard. Poly-1 Copolymer was a hard, amber-colored solid.

[178] Structural Characterization by NMR

[179] The chemical structure of the polymers was confirmed by 'H NMR (Figure 2): benzene ring at 5= 7.16, 8.86 ppm; -CH2-CH2- protons placed between two oxygen units at 5= 4.23, 4.06 ppm; the two protons closed to nitrile group at 5=3.84 ppm; and the protons correlated to -CH2-CH2- of the main chain at 5=2.73 and 1.91 ppm.

[180] Thermal Analysis

[181] Thermal properties reveal significant differences between Poly-1 and Poly-1 Copolymer. As plotted in Figure 3 and Table 1, Poly-1 Copolymer has a lower thermal stability (7A= 189 °C) compared to Poly-1 (7A= 317 °C). The decreased stability is likely due to the presence of acrylic acid units. This data demonstrates that the replacement of acrylic acid with the side chain of the Poly-1 structure promotes thermal stability. In view of the data, Poly-1 exceeds the requirements for SPE processing and operating temperature.

Table 1. Mass loss of Poly-1 and Poly-1 Copolymer at 95% and 90%.

[182] These studies further revealed that both Poly-1 and Poly-1 Copolymer are amorphous, which is a valuable property for SPEs. However, as shown in the DSC thermogram of Figure 4, Poly-1 Copolymer possesses a higher Eg value (57 °C) than Poly- 1 (21 °C). This increase in Tg can be attributed to H-bonding between the hydroxyl groups present in the acrylic acid units and lack of flexibility conferred by the side chains of Poly - 1. Apart from these effects, the presence of hydroxyl groups may originate some instability against lithium metal.

[183] In view of its properties, Poly-1 was selected for further development of SPEs.

[184] Example 2. Solid Polymer Electrolyte (SPE) Processing of Poly-1

[185] Preparation of Poly- 1 Electrolytes

[186] The electrolytes were prepared by a conventional solvent casting method, where Poly-1 was dissolved in a suitable solvent, and subsequently, the specific amount of LiTFSI is added. The resulting electrolyte solution was casted directly on a 16 mm stainless-steel disk with a teflon/Kapton®/silicone O-ring separator. The steps of the electrolyte processing were performed inside an Ar-filled glovebox, according to the procedure outlined in Figure 5.

[187] To find a suitable solvent for SPE processing, the solubility of Poly-1 and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) in different solvents was evaluated (Table 2). Among the solvents tested, acetone was selected due to its lower boiling point.

Table 2. Poly-1 and LiTFSI solubility in different solvents.

[188] Having selected an appropriate solvent, three Poly-1 SPEs consisting of different LiTFSI concentrations were processed. Processed electrolytes prepared according to the disclosed method (see Figure 5) were referred to by the designation Poly-l-X, where X stands for the weight percentage (wt. %) of FiTFSI (Table 3).

Table 3. Electrolyte compositions developed with Poly-1.

[189] Example 3. Characterization of Poly-l-LiTFSI SPEs

[190] Thermal characterization

[191] Thermal properties of the electrolytes were evaluated by TGA and DSC. All electrolytes tested offer high thermal stability (7d,s>300 °C), fulfilling the established thermal requirements. In Figure 6, two degradation steps are observed. The first one at 300 °C is related to Poly-1 decomposition, and the second one corresponds to the decomposition of FiTFSI at 400 °C. Poly-1 SPEs present the same Eg value regardless the content of FiTFSI (Figure 7), and in all the cases a value between 21-25 °C is obtained.

[192] Coordination Environments

[193] In an attempt to elucidate the interaction mechanism between the polymer and the lithium salt, FTIR analysis was employed. Figure 8 depicts the IR spectra for Poly-1 and Poly- 1-25 wt. % FiTFSI. The interaction between the nitrile group and the lithium salt can be observed from the shift of the peak related to the nitrile bond vibration at values around 2240 cm ¹ . In addition, the shift in the vibration mode at 1160 cm ¹ may be attributed to the coordination between ethylene oxide units and lithium cation. Further analysis by Raman spectroscopy or computational studies can be utilized to fully understand the coordination in these SPEs. [194] Electrochemical Characterization

[195] The analysis of the ionic conductivity of Poly- 1 electrolytes shows an ascending trend with the increase of LiTFSI concentration (Figure 9). This variation is decoupled from segmental motion, as the glass transition is not decreased with LiTFSI concentration. Therefore, it is possible that the ionic conductivity occurs via an ion hopping mechanism, as it occurs in polymer-in-salt electrolytes. However, this was not confirmed. Representative ionic conductivity values are compiled in Table 4. The measured ionic conductivity values at high temperatures (100 °C) are in the range of 10 ⁵ S cm ¹ for all designed electrolytes.

Table 4. Thermal properties and ionic conductivity (s) values for Poly-l-LiTFSI electrolyte compositions.

[196] The electrochemical stability of Poly-1 electrolyte samples prepared by the method of Figure 10 was measured at 70 °C. Both studied electrolytes, Poly-1-25 wt. % LiTFSI and Poly- 1-45 wt. % LiTFSI, showed similar profiles, where there is no sign of oxidation up to 4.25 V (vs Li+/Li) (Figure 11). This analysis indicates the suitability of these SPEs for high voltage applications.

[197] Summary

[198] Poly-1 offers high thermal stability as indicated by TGA measurements making it suitable for processing and applying as polymer electrolyte.

[199] Poly-1 contains several polar groups able to dissolve Li-salts.

[200] The bare polymer offers relatively high Tg, which is slightly decreased by plasticizing ability of the LiTFSI. [201] By implementing different chemical modifications of Poly-1 SPEs, these properties and others such as ionic conductivity may be optimized for various battery applications.

[202] Example 4. Characterization of Poly-2

[203] Structural Analysis

[204] Poly-2 Batch 1 and Batch 2 (Figure 12), were dried under vacuum at 70 °C to remove residual solvent.

[205] The dried material was analyzed by NMR to confirm its chemical structure. As shown in Figure 13, the proton signals attributed to -CH2-CH2- placed between the two ester groups at 5= 4.49, 4.32 ppm; and those related to the -CH2-CH- of the main chain around 5= 1.87-1.21 ppm were successfully assigned.

[206] The main functional groups of Poly-2 were also identified by IR spectroscopy, as shown in Figure 14. The carbonyl vibration at 1720 cm-1 and the peaks related to the pyridine ring at 1583 cm ¹ , 1443 cm ¹ , 991 cm ¹ , 744 cm ¹ and 704 cm ¹ were observed.

[207] Thermal Analysis

[208] After confirming the chemical structure, the thermal properties of both polymer batches were analyzed. Thermal stability was tested by TGA, (Figure 15), where no decomposition was observed up to 250 °C. This value is far above the requirements for polymer electrolyte processing or operation. Another important parameter that will impact on the overall performance of a SPE is the thermal transitions. In this case, DSC analysis shows the absence of any melting transition, denoting the amorphous nature of these materials. As shown in Figure 16, similar thermograms are obtained for both batches with a slight difference in the glass transition value, 26 °C (Batch 1) vs. 29 °C (Batch 2), that could be ascribed to the differences in the Mw or PDI.

[209] Example 5. SPE Processing of Poly-2

[210] Electrolyte preparation was carried out by solvent casting method described in Figure 5.

[211] The solubility of Poly-2 and FiTFSI in different solvents was evaluated (Table 5). ACN was initially examined as it is the most common solvent for polymer electrolyte preparation. However, Poly-2 did not dissolve in ACN. Some chlorinated solvents (chloroform, DCM) were then tested, which were effective is solubilizing Poly-2. Since Poly-2 was soluble in chlorinated solvents, and FiTFSI was soluble in ACN, a solvent mixture was utilized to prepare the electrolyte. Among the chlorinated solvent options, DCM was chosen due to lower boiling point (40 °C (DCM) vs. 61 °C (CHCb)). The mixture was optimized and a ratio of ACN:DCM 1 :2 in volume was fixed.

[212] Alternatively, it was confirmed that both Poly-2 and LiTFSI were soluble in DMF. Nevertheless, this solvent was not selected for electrolyte preparation due to the possible difficulties during electrolyte drying owing to the high boiling point of the solvent (153 °C).

Table 5. Poly-2 and LiTFSI solubility in different solvents.

[213] Having defined the solvent mixture, Poly-2 was blended with different LiTFSI concentrations (Table 6). As described above, the processed electrolytes were named as Poly-2-X, where X stands for the weight percentage (wt. %) of LiTFSI. The salt ratios were chosen based on standard PEO/LiTFSI electrolyte, where the most commonly used composition (ethylene oxide (EO)/Li= 20) is equal to 25 wt. % LiTFSI.

Table 6. Electrolyte compositions developed with Poly-2. [214] Within developed Poly-2 based SPEs, two different scenarios were considered: 1) salt-in-polymer electrolyte (SIPE), when low LiTFSI concentration was used; and 2) polymer-in-salt electrolyte (PISE), when the LiTFSI fraction was higher than of the polymer. In SIPE systems, LiTFSI is solvated within the polymer polar groups, whereas in PISE, the LiTFSI is organized in ion clusters. When low LiTFSI concentration was employed, the lithium conduction is dominated by the segmental motion, which means that low glass transition favor the ionic conductivity. Instead, at high LiTFSI concentrations lithium conduction occurs by ion-hopping, decoupled from segmental motion. When analyzing thermal and electrochemical properties, both scenarios were considered.

[215] Thermal characterization of Poly-2-LiTFSI SPEs

[216] Thermal properties of the electrolytes were evaluated by TGA and DSC. Thermogravimetric analysis revealed the adequate thermal stability of all developed electrolytes (Zb above 228 °C, see Figure 17 and Table 5) surpassing the required temperature for safe electrolytes in battery applications. Two step degradation mechanism is observed, the first one around 250 °C related to the polymer degradation and the second one related to LiTFSI decomposition at ~350 °C.

[217] Glass transition evolution was followed by DSC. As depicted in Figure 18, the neat polymer shows a glass transition of 29 °C, and the value continuously increases with the salt concentration increment, with a maximum peak of 55 °C for Poly-2-35 wt. % LiTFSI. This tendency could be attributed to the strong coordination between the polymer and the lithium cation, which is a good indicator of favorable solvating groups presented in Poly- 2. This interaction will be further studied by FTIR analysis. Besides, at high salt concentrations, in Poly-2-45 wt. % LiTFSI and Poly-2-60 wt. % LiTFSI, the glass transition seems to be decreased. This decrease of the Tg value could refer to the saturation of the polar groups present in the electrolyte, resulting in the formation of ion clusters in the system. Therefore, by glass transition analysis, we could identify both scenarios in our system: SIPE until 35 wt. % LiTFSI, and PISE, above 45 wt. % LiTFSI.

[218] The ionic conductivity data is summarized in the Table 7. As expected from DSC analysis, the measured high Tg values are an indicator of the low mobility of polymer chains within the SPE and, thus, restricted ionic conduction. Obtained data from both studies are in good agreement; on the one hand for those where a high Tg is measured (Poly-2-25 wt. %, 35 wt. % and 45 wt. % LiTFSI) the ionic conductivity was out of the range of the detection limit in the studied temperatures (25 - 100 °C). On the other hand, where lower glass transition was determined, (12 wt. %, 16 wt. %, 20 wt. %, 60 wt. % LiTFSI) it was possible to measure the ionic conductivity only at high temperatures. From this analysis and the one related to thermal properties, two ionic conductivity mechanism can be expected. The first one occurs in SIPE (12 wt. % - 35 wt. % LiTFSI) and the segmental motion of the polymer dominates the ionic conductivity. Therefore, in these systems, the high Tg limits the ionic conductivity. The second one occurs in PISE (45 wt. % - 60 wt. % LiTFSI), where the ionic conductivity is decoupled from segmental motion of the polymer, and the ion hopping mechanism predominates the ionic conductivity.

[219] However, the obtained ionic conductivity values are not high enough for practical deployment of SPEs. Poly-2 based SPEs deliver an ionic conductivity in the range of 10 ⁶ S cm ¹ at 100 °C. In addition, when a high salt concentration is used, Poly-2-60 wt. % LiTFSI, an ionic conductivity value of ca. 10 ¹⁰ S cm ¹ can be measured at 60 °C. However, this value is still below the requirements for a SPE.

Table 7. Thermal properties and ionic conductivity values for Poly-2-LiTFSI electrolyte compositions.

[220] Coordination Environment

[221] To further assess the interaction mechanism between Poly-2 and LiTFSI, FTIR- ATR was employed. Two electrolytes were selected for this study, Poly-2-25 wt. % LiTFSI and Poly-2-45 wt. % LiTFSI. The comparison of the neat polymer and the SPEs is shown in Figure Ib-Ic, where the most representative groups of the polymer are highlighted (see Figure la). The carbonyl group vibration at 1720 cm ¹ (highlighted with the red line) is shifted to lower wavenumber values in the case of the SPEs as a result of the coordination with the lithium cation. Regarding the pyridine group, an interaction with lithium cation can be also predicted due to some fluctuations in the value of the peaks (at 1583, 1443, 991, 744, 704 cm ¹ ). The possible coordination mechanisms between the polymer matrix and LiTFSI are depicted in Figure 19. These interactions may restrict the freedom of movement of polymer chains, and may explain the observed Tg increase (Figure H). As mentioned above, other techniques such as Raman spectroscopy or computational studies could be utilized to further develop an understanding of the conduction mechanism of these SPEs.

[222] Summary

[223] Poly-2 shows high thermal stability as proven by TGA making it suitable for processing at high temperatures and application as safe polymer electrolyte.

[224] Poly-2 contains several polar groups able to dissolve Li-salts. The capability of Poly-2 to coordinate with Li+ was confirmed by the increase of the Tg and by FTIR, where a shift of the peaks assigned to the main polymer groups was observed.

[225] Example 6. Comparison of Poly-1 and Poly-2 to Literature SPEs

[226] The chemical and physical properties of Poly- 1 and Poly-2 based electrolytes were compared to other SPEs found in the literature (Table 8). Polyethylene (PEO) and its derivatives are the most studied polymer matrixes. The most similar reported structures compared to Poly-1 and Poly-2 have been selected and listed together with the two studied polymers for a comparison among the species.

Table 8. Comparison of Poly-1 and Poly-2 properties to literature SPEs.

POLY-l= Poly(phenylacetonitrile acrylate); POLY-2= Poly(picolinate acrylate); PEO= Polyethylene oxide); POEM= Poly(oligo- oxyethylene methacrylate); PS-6-(PS-g-PEO)-6-PS= Polystyrene-poly(ethylene oxide) block-graft copolymer, PAN= Poly(acrylonitrile); PCEA= Poly(2-cyanoethylacrylate); PCYAMEO= Poly(3-(2-cyanoethoxymethyl)-3-ethyloxetane); PMMA= Poly(methylmethacrylate); PBuA= Poly(Butyl acrylate); P(AN co-BuA)= Poly(acrylonitrile-Poly(butyl acrylate) copolymer; P(Phe- GEC)= Poly(carbonate-phenyl glycidyl ether); PS-b-P2VP= Polystyrene-block-poly(2-vinylpyridine); (a) Oxidation potential measured by LSV at 70 °C; (b) n.r. = not reported (c) T _m- 62 °C; (d) T _m- 17 °C (e) Measured at 90 °C; (f) Polymer-in-salt electrolytes (salt concentrations greater than 50 wt%).

[227] The solvent-free electrolytes included in Table 8 include a mixture of polymer and Li salt without the addition of any solvent, filler or plasticizer.

[228] Among all the SPEs, PEO is the most employed polymer matrix due to its high salt solubility and mechanical stability. However, PEO-based SPEs usually suffer from low ionic conductivity at temperatures below Tm due to its high crystalline nature, as well as low voltage stability (below 4.0 V vs Li ₊ /Li) hampering their practical application. For these reasons, efforts have been undertaken to develop polymer matrixes with alternative functional groups with the aim of improving the anodic stability, as well as, decreasing the crystallinity, and leading to a battery with a wider temperature operation range. Accordingly, the properties shown in Table 8 have been selected for the analysis.

[229] The listed SPEs can be grouped according to the following criteria: (i) polymer matrices studied in this report (entries 1 and 2); (ii) PEO and PEO derivatives (entries 3 to 5); (iii) poly(acrylonitrile) (PAN) and PAN derivatives (entries 6-8); (iv) poly(acrylate) derivatives (entries 9 to 11) and (v) polymers with aromatic pendant groups (entries 12 and 13). The chemical structure of these materials can be seen in Figure 20.

[230] LiTFSI was selected as a conducting salt due to its solubility in polymer matrices and subsequent plasticizing effect, and its excellent chemical, thermal and electrochemical stability. A number of the entries in the table employ LiTFSI as a conducting salt, confirming its predominant use for SPEs.

[231] As shown in Table 8, the Tg of PEO and PEO-derivatives SPEs (entries 3 to 5) are less that the values measured for Poly-1 and Poly-2.

[232] Additionally, at the same lithium salt concentration (25 wt. % LiTFSI), the conductivity is higher for PEO-based electrolytes compared to Poly-1 and Poly-2. Nevertheless, the anodic stability of Poly-l/LiTFSI SPE measured at 70 °C shows an oxidation potential of about 4.2 V vs. Li ₊ /Li, which is higher than the values reported for PEO and PS-Z>-(PS-g-PEO)-Z>-PS. This suggests that decreasing the Tg of Poly-1 by different means, would provide an electrolyte that may be suitable for use in high voltage technology.