Aqueous ZN-tetrazine batteries

Abstract

The present disclosure provides a battery comprising: a Zn-based anode material; and a cathode material comprising a compound having a structure of Formula (I) and / or Formula (II). Systems and articles comprising one or more of said batteries are also provided. A method of making a battery is also provided.

Description

AQUEOUS ZN-TETRAZINE BATTERIESCROSS-REFERENCE TO RELATED APPLICATIONSThis application claims the benefit of priority to United States Provisional Patent Application No. 63 / 598,279 filed November 13, 2023, the disclosure of which is incorporated herein by reference in its entirety.STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENTThis invention was made with government support under 2124604, awarded by the National Science Foundation. The government has certain rights in the invention.TECHNICAL FIELDThis application relates generally to cathode materials that can be used in Zn-based batteries.BACKGROUNDAqueous zinc ion batteries (AZIBs) are a class of promising grid-scale energy storage systems due to their inherent safety and low cost. The high theoretical capacity (820 mAh g'1), stability, and low toxicity of zinc metal make it an ideal anode material for AZIBs. Conventional cathode materials in AZIBs are based on inorganic metal materials, e.g., manganese oxides, vanadium oxides, and Prussian blue analogs. However, supply chain issues and high costs associated with transition metals limit their adoption into grid-scale energy storage.Thus, new cathodic materials are needed. These needs and other needs are at least partially satisfied by the present disclosure.SUMMARYThe present disclosure provides batteries, systems comprising one or more of said batteries, and articles comprising one or more of said batteries. Methods of making said batteries are also provided.In one aspect, a battery is provided. In some aspects, in addition, or alternative to any disclosed herein aspects, the battery comprises a Zn-based anode material. In some aspects, in addition, or alternative to any disclosed herein aspects, the batter comprises a cathode material comprising a compound having a structure of Formula (I) and / or Formula (II):tautomer thereof, wherein all variables are as defined herein.In another aspect, a system is provided. In some aspects, in addition, or alternative to any disclosed herein aspects, the system comprises one or more of the batteries described herein.In another aspect, an article is provided. In some aspects, in addition, or alternative to any disclosed herein aspects, the article comprises one or more of the batteries described herein.In another aspect, a method of making a battery is provided. In some aspects, in addition, or alternative to any disclosed herein aspects, the method comprises providing a Zn- based anode. In some aspects, in addition, or alternative to any disclosed herein aspects, the method comprises providing a cathode material comprising a compound having a structure of Formula (I) and / or Formula (II) as described herein. In some aspects, in addition, or alternative to any disclosed herein aspects, the method comprises providing an electrolyte.Other systems, methods, features and / or advantages will be or may become apparent to one with skill in the art upon examination of the following drawings and detailed description. It is intended that all such additional systems, methods, features and / or advantages be included within this description and be protected by the accompanying claims.DESCRIPTION OF DRAWINGSFIGs. 1A-1B depict a comparison of sequential and cooperative Zn2+ / H+coinsertion mechanisms and the representative voltage profiles of (FIG. 1A) OEMs in AZIBs withconventional quinone and / or imine-based motifs (FIG. IB) tetrazine cathode materials reported in the experimental examples.FIG. 2 depicts representative structures of tetrazine derivatives investigated as cathodes in AZIB in the experimental examples.FIG. 3 depicts (panel A) three-electrode solution CV of 4 with 0.1 M TBACICh in MeCN and 0.1 M TBACIO4 + 0.01 M Zn(OTf)2 in MeCN and (panel B) three-electrode solid- state CV of Zn-4 with 3 M Zn(OTf)2 as the electrolyte and with pH 4 HOTf as the electrolyte.FIGs. 4A-4C depict (FIG. 4A) Galvanostatic charge discharge profile of Zn-4 cells, (FIG. 4B) variable rate performance, and (FIG. 4C) long-term cycling stability.FIG. 5 depicts Ragone plot comparing the performance of 4 to state-of-the-art inorganic and organic cathodes in AZIBs.|8 3‘46 5()|FIGs. 6A-6D depict (FIG. 6A) GCD profile of 4 and (FIG. 6B) XRF, (FIG. 6C) IR, and (FIG. 6D) PXRD analysis of pristine, discharge state, and charge state of cathode 4. The stars in PXRD profile denote the features of Znx(OTf)y(OH)2X-y’(H2O)n.FIG. 7 depicts a SEM image (top left) with corresponding EDX signal mapping of N, F, and Zn atoms for discharge state 4-Zn-H.FIG. 8 depicts a proposed but non-limiting mechanism for the redox of 4 in AZIB.FIG. 9 depicts powder X-ray diffraction data of discharged 4 after washing with DCM to reveal peaks related to Znx(OTf)y(OH)2xy*(H2O)n. Due to the amorphous nature of Znx(OTf)y(OH)2xy*(H2O)n, there has been some ambiguity in its exact assignment. The provided spectrum should contain only phases related to Znx(OTf)y(OH)2xy*(H2O)n and was used to assign relevant species in discharged 4 in combination with previous literature reports.FIGs. 10A-10B depict powder X-ray diffraction pattern of (FIG. 10A) pristine 4, 50% discharged 4, and 100% discharged 4 along with Znx(OTf)y(OH)2xy*(H2O)n for comparison and (FIG. 10B) pristine 4, 100% discharged 4, 100% charged 4, and 4-Hi.FIGs. 11A-11B depict (FIG. 11 A) low-magnified cross-sectional SEM images of the discharged state of 4 with corresponding EDX signal mapping images of respective atoms. The resulting cross-sectional SEM image combined with elemental mapping reveals the abundant presence of Zn element throughout the entire cross-sectional area of the electrode, indicating aZn-related discharge process and (FIG. 11B) surface SEM and EDX analysis containing flakelike morphology consistent with Znx(OTf)y(OH)2xy*(H2O)n.FIG. 12 depicts postmortem SEM analysis of charged 4. The ca. 5 um-sized crystal of charged 4 maintains its morphology after cycling.FIG. 13 depicts SEM image (top left) with corresponding EDX signal mapping of N, F, and Zn atoms for discharge state 4-Zn-H.FIGs. 14A-14D depict XRF spectra of cathode powder (FIG. 14A) pristine 4, (FIG. 14B) 50% discharged 4, and (FIG. 14C) 100% discharged 4, and (FIG. 14D) the charged 4 cathode powders.FIG. 15 depicts an overlay of IR spectra of pristine 4 cathode powder, discharged 4 cathode powder, and discharged 4 after extraction of organic material with DCM to assess Znx(OTf)y(OH)2x-y*(H2O)n formation.FIG. 16 is a digital photo of free-standing cathode adhered to stainless steel current collector.FIGs. 17A-17B depict (FIG. 17A) galvanostatic charge-discharge curves and (FIG. 17B) cycling data of 1 in 3 MZnSCh at a rate of 1C (198 mAg'1). DMP stands for 3,5-dimethyl- pyrazole and inlet digital photo of the separator postcycling.FIGs. 18A-18B depict (FIG. 18 A) galvanostatic charge-discharge curves and (FIG. 18B) cycling data of 2 in 3 M ZnSCh at a rate of 1C (377 mA g'1). Inlet digital photo of the separator post-cycling.FIG. 19 depicts galvanostatic charge-discharge curves of 3 in 3 M ZnSCh at a rate of 1C (377 mA g-1). Inlet digital photo of the separator post-cycling. Long-term cycling was not performed due to unlimited charging capacity, indicative of redox shuttling.FIGs. 20A-20B depict (FIG. 20A) galvanostatic charge-discharge curves and (FIG. 20B) cycling data of 5 in 3 M ZnSCh at a rate of 1C (311 mA g'1) and inlet digital photo of the separator post-cycling.FIGs. 21A-21B depict (FIG. 21A) galvanostatic charge-discharge curves and (FIG. 2 IB) cycling data of 6 in 3 M ZnSCh at a rate of 1C (288 mA g'1). Inlet digital photo of the separator post-cycling.FIG. 22 provides a comparison of capacity retained over 30 cycles of 4, 5, and 6.FIGs. 23 A-23B depict (FIG. 23 A) long-term cycling GCD profile evolution from cycle 1, cycle 10, cycle 100, and cycle 500 of 4 at 1C (229 mA g’1) with 3 M Zn(OTf)2 as the electrolyte with respective voltage hysteresis and (FIG. 23B) the first cycle of 4 with varying loading of active material at 0.1C (22.9 mA g’1) with 3 M Zn(OTf)2 as the electrolyte.FIGs. 24A-24B provide a comparison of the GCD profile in 3 M Zn(OTf)2 and respective electrochemical reactions of Zn cells of (FIG. 24A) 4-H2 and (FIG. 24B) 4.FIG. 25 depicts a GITT profile of 4 in 3 M Zn(OTf)2.FIGs. 26A-26B depict (FIG. 26A) solid-state variable rate CV of 4 at 0.2 mV s’1, 0.4 mV s’1, 0.8 mV s’1, 1.2 mV s’1, 1.6 mV s’1, and (FIG. 26B) power law fitting with the corresponding plots of log(z) vs. log(v) for oxidation and reduction.FIG. 27 is a digital picture of disassembled electrode of 4 covered with separator.FIG. 28 depicts how XRD structure of 4 shows extended columns packed through 7t-7t stacking.Like reference symbols in the various drawings indicate like elements.DETAILED DESCRIPTIONIt is appreciated that certain features of the disclosure, which are, for clarity, described in the context of separate aspects, can also be provided in combination with a single aspect. Conversely, various features of the disclosure, which are, for brevity, described in the context of a single aspect, can also be provided separately or in any suitable subcombination. 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.The present invention can be understood more readily by reference to the following detailed description, examples, drawings, and claims, and their previous and following description. However, before the present articles, systems, and / or methods are disclosed and described, it is to be understood that this invention is not limited to the specific or exemplary aspects of articles, systems, and / or methods disclosed unless otherwise specified, as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.The following description of the invention is provided as an enabling teaching of the invention in its best, currently known aspect. To this end, those skilled in the relevant art will recognize and appreciate that many changes can be made to the various aspects of the invention described herein while still obtaining the beneficial results of the present invention. It will also be apparent that some of the desired benefits of the present invention can be obtained by selecting some of the features of the present invention without utilizing other features. Accordingly, those of ordinary skill in the pertinent art will recognize that many modifications and adaptations to the present invention are possible and may even be desirable in certain circumstances and are a part of the present invention. Thus, the following description is again provided as illustrative of the principles of the present invention and not in limitation thereof.As used herein, the terms "optional" or "optionally" mean that the subsequently described event or circumstance can or cannot occur and that the description includes instances where said event or circumstance occurs and instances where it does not.It is appreciated that certain features of the disclosure, which are, for clarity, described in the context of separate aspects, can also be provided in combination with a single aspect. Conversely, various features of the disclosure, which are, for brevity, described in the context of a single aspect, can also be provided separately or in any suitable subcombination.As used in the description and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, a reference to “a solvent” includes not only one but also two or more such solvents, and a reference to “a battery” includes not only one but also two or more such batteries and the like.Throughout the description and claims of this specification, the word "comprise" and other forms of the word, such as "comprising" and "comprises," are open, non-limiting terms and mean “including but not limited to,” and are not intended to exclude, for example, other additives, segments, integers, or steps. Furthermore, it is to be understood that the terms “comprise,” “comprising,” and “comprises” as they relate to various aspects, elements, and features of the disclosed invention also include the more limited aspects of "consisting essentially of and "consisting of."For the terms "for example" and "such as," and grammatical equivalences thereof, the phrase "and without limitation" is understood to follow unless explicitly stated otherwise. It is further understood that these phrases are used for explanatory purposes only. It is furtherunderstood that the term "exemplary," as used herein, means "an example of and is not intended to convey an indication of a preferred or ideal aspect.The expressions "ambient temperature" and "room temperature" as used herein are understood in the art and refer generally to a temperature from about 20 °C to about 35 °C.Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Furthermore, when numerical ranges of varying scope are set forth herein, it is contemplated that any combination of these values, inclusive of the recited values, may be used. Further, ranges can be expressed herein as from “about” one particular value and / or to “about” another particular value. When such a range is expressed, another aspect includes from the one particular value and / or to the other particular value.Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint and independently of the other endpoint. Unless stated otherwise, the term “about” means within 5% (e.g., within 2% or 1%) of the particular value modified by the term “about.”Throughout this disclosure, various aspects of the invention can be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, a description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as individual numbers within that range, for example, 1, 2, 2.7, 3, 4, 5, 5.3, 6 and any whole and partial increments therebetween. This applies regardless of the breadth of the range.In still further aspects, when the specific values are disclosed between two end values, it is understood that these end values can also be included.In still further aspects, when the range is given, and exemplary values are provided, it is understood that any ranges can be formed between any exemplary values within the broadest range.As used herein, the term “composition” is intended to encompass a product comprising the specified ingredients in the specified amounts, as well as any product that results, directly or indirectly, from a combination of the specified ingredients in the specified amounts.References in the specification and concluding claims to parts by weight of a particular element or component in a composition denote the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight is expressed. Thus, in a mixture containing 2 parts by weight of component X and 5 parts by weight, components Y, X, and Y are present at a weight ratio of 2:5 and are present in such a ratio regardless of whether additional components are contained in the mixture.A weight percent (wt.%) of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.It will be understood that when an element is referred to as being "connected" or "coupled" to another element, it can be directly connected or coupled to the other element, or intervening elements may be present. In contrast, when an element is referred to as being "directly connected" or "directly coupled" to another element, there are no intervening elements present. Other words used to describe the relationship between elements or layers should be interpreted in a like fashion (e.g., "between" versus "directly between," "adjacent" versus "directly adjacent," "on" versus "directly on").As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.It will be understood that the terms "first," "second," etc., may be used herein to describe various elements, components, regions, layers, and / or sections. These elements, components, regions, layers, and / or sections should not be limited by these terms. These terms are only used to distinguish one element, component, region, layer, or section from another element, component, region, layer, or section. Thus, a first element, component, region, layer, or section discussed below could be termed a second element, component, region, layer, or section without departing from the teachings of example embodiments.As used herein, the term "substantially" means that the subsequently described event or circumstance completely occurs or that the subsequently described event or circumstance generally, typically, or approximately occurs.Still further, the term "substantially" can, in some aspects, refer to at least about 90 %, at least about 95 %, at least about 99 %, or about 100 % of the stated property, component, composition, or other condition for which substantially is used to characterize or otherwise quantify an amount.In other aspects, as used herein, the term “substantially free,” when used in the context of a composition or component of a composition that is substantially absent, is intended to refer to an amount that is then about 1 % by weight, e.g., less than about 0.5 % by weight, less than about 0.1 % by weight, less than about 0.05 % by weight, or less than about 0.01 % by weight of the stated material, based on the total weight of the composition.As used herein, the terms “substantially identical reference composition,” “substantially identical reference article,” or “substantially identical reference electrochemical cell” refer to a reference composition, article, or electrochemical cell comprising substantially identical components in the absence of an inventive component. In another exemplary aspect, the term "substantially," in, for example, the context "substantially identical reference composition," or “substantially identical reference article,” or “substantially identical reference electrochemical cell,” refers to a reference composition, article, or an electrochemical cell comprising substantially identical components and wherein an inventive component is substituted with a common in the art component.The organic moieties mentioned when defining variable positions within the general formulae described herein (e.g., the term “halogen”) are collective terms for the individual substituents encompassed by the organic moiety. The prefix Cn-m preceding a group or moiety indicates, in each case, the possible number of carbon atoms in the group or moiety that follows.The term “ion,” as used herein, refers to any molecule, portion of a molecule, a cluster of molecules, molecular complex, moiety, or atom that contains a charge (positive, negative, or both at the same time within one molecule, cluster of molecules, molecular complex, or moiety (e.g., zwitterions)) or that can be made to contain a charge. Methods for producing a charge in a molecule, a portion of a molecule, a cluster of molecules, a molecular complex, moiety, or atom are disclosed herein and can be accomplished by methods known in the art,e.g., protonation, deprotonation, oxidation, reduction, alkylation, acetylation, esterification, de- esterification, hydrolysis, etc.The term “anion” is a type of ion and is included within the meaning of the term “ion.” An “anion” is any molecule, portion of a molecule (e.g., zwitterion), a cluster of molecules, molecular complex, moiety, or atom that contains a net negative charge or that can be made to contain a net negative charge. The term “anion precursor” is used herein to specifically refer to a molecule that can be converted to an anion via a chemical reaction (e.g., deprotonation).The term “cation” is a type of ion and is included within the meaning of the term “ion.” A “cation” is any molecule, portion of a molecule (e.g., zwitterion), a cluster of molecules, molecular complex, moiety, or atom containing a net positive charge or that can be made to contain a net positive charge. The term “cation precursor” is used herein to specifically refer to a molecule that can be converted to a cation via a chemical reaction (e.g., protonation or alkylation).The term “electrolyte composition,” as used herein, refers to a chemical composition suitable for use as an electrolyte in an electrochemical cell.The term “electrolyte salt,” as used herein, refers to an ionic salt that is at least partially soluble in an electrolyte and that at least partially dissociates into ions in the electrolyte.The term “anode” refers to an electrode of an electrochemical cell at which oxidation occurs. In a galvanic cell, such as a battery, the anode is the negative electrode. In a secondary (i.e., rechargeable) battery, the anode is the electrode at which oxidation occurs during discharge and reduction occurs during charging.The term “cathode” refers to an electrode of an electrochemical cell at which reduction occurs. In a galvanic cell, such as a battery, the cathode is the positive electrode. In a secondary (i.e., rechargeable) battery, the cathode is the electrode at which reduction occurs during discharge and oxidation occurs during charging.In still further aspects, the term state of charge (SOC) refers to the level of charge of a battery relative to its capacity. SOC is usually expressed as a percentage (0% = empty; 100% = full). An alternative form of the same measure can be referred to as a depth of discharge (DOD), calculated as 100 - SoC (100% = empty; 0% = full). SOC is normally used when discussing the current state of a battery in use, while DOD is most often seen when discussing the lifetime of the battery after repeated use. In still further aspects, the term “deep discharge”refers to a condition where the state of charge (SOC) of the battery is substantially 0%. Yet, in other aspects, the term “deep charge” refers to a condition where the SOC of the battery is substantially 100%.As used herein, the term “substituted” means that a hydrogen atom is removed and replaced by a substituent. It is contemplated to include all permissible substituents of organic compounds. As used herein, the phrase "optionally substituted" means unsubstituted or substituted. It is understood that substitution at a given atom is limited by valency. In a broad aspect, the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents can be one or more and the same or different for appropriate organic compounds. For purposes of this disclosure, the heteroatoms, such as nitrogen, can have hydrogen substituents and / or any permissible substituents of organic compounds described herein that satisfy the valencies of the heteroatoms. This disclosure is not intended to be limited in any manner by the permissible substituents of organic compounds. Also, the terms “substitution” or “substituted with” includes the implicit proviso that such substitution is in accordance with a permitted valence of the substituted atom and the substituent and that the substitution results in a stable compound, e.g., a compound that does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. In still further aspects, it is understood that when the disclosure describes a group being substituted, it means that the group is substituted with one or more (i.e., 1, 2, 3, 4, or 5) groups as allowed by valence selected from alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycle, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, cyano, azido, oxo, silyl, sulfo-oxo, sulfonyl, sulfone, sulfonylamino, sulfoxide, or thiol, as described below.The terms for various functional groups as used herein are not intended to be limited to monovalent radicals and may include polyvalent radical groups as appropriate, such as divalent, trivalent, tetravalent, pentavalent, and hexavalent groups, and the like, based on the position and location of such groups in the compounds described herein as would be readily understood by the skilled person.“Z1,” “Z2,” “Z3,” and “Z4” are used herein as generic symbols to represent various specific substituents. In certain aspects, the generic symbols to represent various specificsubstituents can be marked as “R1,” “R2,” “R3,” or “Rn” wherein n is a subsequent number of substituents. These symbols can be any substituent, not limited to those disclosed herein, and when they are defined to be certain substituents in one instance, they can, in another instance, be defined as some other substituents.A dashthat is not between two letters or symbols is used to indicate a point of attachment for a substituent. For example, -(C=0)NH2 is attached through the carbon of the keto (C=O) group.The term “aliphatic,” as used herein, refers to a non-aromatic hydrocarbon group and includes branched and unbranched, alkyl, alkenyl, or alkynyl groups. As used herein, the term "Cn-Cm alkyl" (or “Cn-m”) employed alone or in combination with other terms refers to a saturated hydrocarbon group that may be straight-chain or branched, having n to m carbons. It is understood that the terms Cn-m and Cn-Cm can be used interchangeably and just to show that the specific compound has between n to m carbons. Unless otherwise specified, C1-C24 (e.g., C1-C22, C1-C20, Ci-Cis, C1-C16, C1-C14, C1-C12, C1-C10, Ci-C8, C1-C6, or C1-C4) alkyl groups are intended. Examples of alkyl moieties include, but are not limited to, chemical groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, sec-butyl; higher homologs such as 2-methyl-l-butyl, n-pentyl, 3 -pentyl, n-hexyl, 1,2,2-trimethylpropyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl, and the like. The alkyl group can also be substituted or unsubstituted. Throughout the specification, “alkyl” is generally used to refer to both unsubstituted alkyl groups and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituent(s) on the alkyl group. The alkyl group can be substituted with one or more groups including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, or thiol, as described below, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied. It is further understood that throughout the specification, “alkyl” can also be referred to as a linking group of saturated hydrocarbons that are divalent radicals. In other words, in a broader description, the term “alkyls” also encompasses alkylenes. It is further understood that the term “alkyl” covers saturated hydrocarbons that are multivalent radicals.The term "heteroaliphatic" refers to an aliphatic moiety that contains at least one heteroatom in the chain, for example, an amine, carbonyl, carboxy, oxo, thio, phosphate,phosphonate, nitrogen, phosphorus, silicon, or boron atoms in place of a carbon atom. In certain aspects, the only heteroatom is nitrogen. In certain aspects, the only heteroatom is oxygen. In certain aspects, the only heteroatom is sulfur. “Heteroaliphatic" is intended herein to include, but is not limited to, heteroalkyl, heteroalkenyl, heteroalkynyl, heterocycloalkyl, heterocycloalkenyl, and heterocycloalkynyl moieties. In certain aspects, "heteroaliphatic" is used to indicate a heteroaliphatic group (cyclic, acyclic, substituted, unsubstituted, branched, or unbranched) having 1-20 carbon atoms. In certain aspects, the heteroaliphatic group is optionally substituted in a manner that results in the formation of a stable moiety. Nonlimiting examples of heteroaliphatic moieties are polyethylene glycol, polyalkylene glycol, amide, polyamide, polylactide, polyglycolide, thioether, and ether, alkyl-heterocycle-alkyl, -O-alkyl- O-alkyl, alkyl-O-haloalkyl, etc.Throughout the specification, “alkyl” is generally used to refer to both unsubstituted alkyl groups and substituted alkyl groups; however, substituted alkyl groups are also specifically referred to herein by identifying the specific substituent(s) on the alkyl group.For example, the term “halogenated alkyl” specifically refers to an alkyl group that is substituted with one or more halides, e.g., fluorine, chlorine, bromine, or iodine. “Haloalkyl” is a branched or straight-chain alkyl group substituted with 1 or more halo atoms described above, up to the maximum allowable number of halogen atoms. Examples of haloalkyl groups include but are not limited to, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, pentafluoroethyl, heptafluoropropyl, difluorochloromethyl, di chlorofluoromethyl, difluoroethyl, difluoropropyl, di chloroethyl, and di chloropropyl. “Perhaloalkyl” means an alkyl group having all hydrogen atoms replaced with halogen atoms. Examples include but are not limited to trifluoromethyl and pentafluoroethyl.The term “alkoxyalkyl” specifically refers to an alkyl group that is substituted with one or more alkoxy groups, as described below. The term “alkylamino” specifically refers to an alkyl group that is substituted with one or more amino groups, as described below and the like. When “alkyl” is used in one instance, and a specific term such as “alkylalcohol” is used in another, it is not meant to imply that the term “alkyl” does not also refer to specific terms such as “alkylalcohol” and the like.As used herein, "Cn-Cm alkenyl" refers to an alkyl group having one or more double carbon-carbon bonds and having n to m carbons. Alkenyls can be straight-chained or branched.Unless otherwise specified, C2-C24 (e.g., C2-C22, C2-C20, C2-C18, C2-C16, C2-C14, C2-C12, C2- C10, C2-C8, C2-C6, or C2-C4) alkenyl groups are intended. Alkenyl groups may contain more than one unsaturated bond. Examples include ethenyl, 1 -propenyl, 2-propenyl, 1- methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-l-propenyl, 2-methyl-l -propenyl, 1- methyl-2-propenyl, 2-methyl-2-propenyl, 1 -pentenyl, 2-pentenyl, 3 -pentenyl, 4-pentenyl, 1- methyl- 1-butenyl, 2-methyl-l -butenyl, 3 -methyl- 1-butenyl, l-methyl-2-butenyl, 2-methyl-2- butenyl, 3-methyl-2-butenyl, 1 -methyl-3 -butenyl, 2-methyl-3-butenyl, 3 -methyl-3 -butenyl, l,l-dimethyl-2-propenyl, 1,2-dimethyl-l-propenyl, l,2-dimethyl-2-propenyl, 1-ethyl-l- propenyl, l-ethyl-2-propenyl, 1 -hexenyl, 2-hexenyl, 3 -hexenyl, 4-hexenyl, 5-hexenyl, 1- methyl- 1 -pentenyl, 2-m ethyl- 1 -pentenyl, 3 -methyl - 1 -pentenyl, 4-m ethyl- 1 -pentenyl, 1- methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1- methyl-3 -pentenyl, 2-methyl-3 -pentenyl, 3 -methyl-3 -pentenyl, 4-m ethyl-3 -pentenyl, 1- methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 11 ,1- dimethyl-2-butenyl, l,l-dimethyl-3 -butenyl, 1,2-dimethyl- 1-butenyl, l,2-dimethyl-2-butenyl, l,2-dimethyl-3 -butenyl, 1,3 -dimethyl- 1-butenyl, l,3-dimethyl-2-butenyl, 1,3 -dimethyl -3- butenyl, 2, 2-dimethyl-3 -butenyl, 2,3 -dimethyl- 1-butenyl, 2,3-dimethyl-2-butenyl, 2,3- dimethyl-3 -butenyl, 3,3-dimethyl-l-butenyl, 3,3-dimethyl-2-butenyl, 1 -ethyl- 1-butenyl, 1- ethyl-2-butenyl, 1 -ethyl-3 -butenyl, 2-ethyl- 1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, l,l,2-trimethyl-2-propenyl, 1 -ethyl- l-methyl-2-propenyl, l-ethyl-2-methyl-l -propenyl, and 1- ethyl-2-methyl-2-propenyl. The term “vinyl” refers to a group having the structure -CEUCH2; 1 -propenyl refers to a group with the structure -CEUCH-CH3; and 2-propenyl refers to a group with the structure -CH2-CEUCH2. Asymmetric structures such as (Z1Z2)C=C(Z3Z4) are intended to include both the E and Z isomers. This can be presumed in structural formulae herein wherein an asymmetric alkene is present, or it can be explicitly indicated by the bond symbol C=C. Examples of alkenyl groups include, but are not limited to, ethenyl, n-propenyl, isopropenyl, n-butenyl, seobutenyl, and the like. In various aspects, the alkenyl moiety contains 2 to 6, 2 to 4, or 2 to 3 carbon atoms. The alkenyl group can be substituted with one or more groups including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, cyano, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, thiol, or phosphonyl, as described below. It is understood that alkenyl groups can be used as a linking group, in such aspects, the broad definition of the alkenyl group also includes divalent alkenylene groups.As used herein, "Cn-Cm alkynyl" refers to an alkyl group having one or more triple carbon-carbon bonds and having n to m carbons. Alkynyls can be straight-chained or branched hydrocarbon moieties containing a triple bond. Unless otherwise specified, C2-C24 (e.g., C2- C24, C2-C20, C2-C18, C2-C16, C2-C14, C2-C12, C2-C10, C2-C8, C2-C6, or C2-C4) alkynyl groups are intended. Alkynyl groups may contain more than one unsaturated bond. Examples include C2- Ce-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl (or propargyl), 1-butynyl, 2-butynyl, 3- butynyl, l-methyl-2-propynyl, 1 -pentynyl, 2-pentynyl, 3 -pentynyl, 4-pentynyl, 3 -methyl- 1- butynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, l,l-dimethyl-2- propynyl, l-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 3- m ethyl- 1 -pentynyl, 4-methyl-l -pentynyl, l-methyl-2-pentynyl, 4-methyl-2-pentynyl, 1- methyl-3 -pentynyl, 2-methyl-3 -pentynyl, l-methyl-4-pentynyl, 2-methyl-4-pentynyl, 3- methyl-4-pentynyl, l,l-dimethyl-2-butynyl, l,l-dimethyl-3-butynyl, l,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3, 3 -dimethyl -1-butynyl, l-ethyl-2-butynyl, l-ethyl-3-butynyl, 2- ethyl-3-butynyl, and l-ethyl-l-methyl-2-propynyl. In various aspects, the alkynyl moiety contains 2 to 6, 2 to 4, or 2 to 3 carbon atoms. The alkynyl group can be substituted with one or more groups including, but not limited to, alkyl, halogenated alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halide, hydroxy, ketone, nitro, cyano, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl, as described below.As used herein, the term "Cn-Cm alkylene," employed alone or in combination with other terms, refers to a divalent alkyl linking group having n to m carbons. Examples of alkylene groups include, but are not limited to, ethan-l,2-diyl, propan- 1,3 -diyl, propan- 1,2- diyl, butan-l,4-diyl, butan-1,3 -diyl, butan-l,2-diyl, 2-methyl-propan-l,3-diyl, and the like. In various aspects, the alkylene moiety contains 2 to 6, 2 to 4, 2 to 3, 1 to 6, 1 to 4, or 1 to 2 carbon atoms. It is understood that in certain aspects, alkylene can also be referred to as alkyl in a broader scope of the definition, with the understanding that if it is a linking group, it provides two bonds.As used herein, the term “Cn-Cm alkoxy,” employed alone or in combination with other terms, refers to a group of formula -O-alkyl, wherein the alkyl group has n to m carbons. In other words, the term alkoxy, as used herein, is an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group can be defined as a group of the formula Z'-O-, where Z1is unsubstituted or substituted alkyl as defined above. Unless otherwise specified, alkoxy groups wherein Z1is a C1-C24 (e.g., C1-C22, C1-C20, Ci-Cis, C1-C16, C1-C14, C1-C12, C1-C10, Ci-Cs, Ci-Ce, or C1-C4) alkyl group are intended. Examples include methoxy, ethoxy, propoxy, 1- m ethyl-ethoxy, butoxy, 1-methyl-propoxy, 2-methyl-propoxy, 1,1 -dimethyl-ethoxy, pentoxy, 1-methyl-butyloxy, 2-methyl-butoxy, 3-methyl-butoxy, 2,2-di-methyl-propoxy, 1 -ethylpropoxy, hexoxy, 1,1-dimethyl-propoxy, 1,2-dimethyl-propoxy, 1-methyl-pentoxy, 2-methyl- pentoxy, 3-methyl-pentoxy, 4-methyl-penoxy, 1,1-dimethyl-butoxy, 1,2-dimethyl-butoxy, 1,3- dimethyl-butoxy, 2,2-dimethyl-butoxy, 2,3-dimethyl-butoxy, 3,3-dimethyl-butoxy, 1 -ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethyl-propoxy, 1,2,2-trimethyl-propoxy, 1 -ethyl- 1-methyl- propoxy, and l-ethyl-2-methyl-propoxy. In other aspects, an example of alkoxy groups includes methoxy, ethoxy, propoxy (e.g., n-propoxy and isopropoxy), tert-butoxy, and the like. In various aspects, the alkyl group has 1 to 6, 1 to 4, or 1 to 3 carbon atoms.The term “cyclic group” is used herein to refer to either aryl groups or non-aryl groups (z.e., cycloalkyl, heterocycloalkyl, cycloalkenyl, and heterocycloalkenyl groups), or both. Cyclic groups have one or more ring systems that can be substituted or unsubstituted. A cyclic group can contain one or more aryl groups, one or more non-aryl groups, or one or more aryl groups and one or more non-aryl groups. It is understood that if this cyclic group is a linking group, aryl groups can include broader scope arylenes if they behave as linking groups.As used herein, “aryl” refers to a radical of a monocyclic or polycyclic (e.g., bicyclic or tricyclic) 4n+2 aromatic ring system (e.g., having 6, 10, or 14 it electrons shared in a cyclic array) having 6-14 ring carbon atoms and zero heteroatoms provided in the aromatic ring system (“Ce-14 aryl”). In some aspects, an aryl group has 6 ring carbon atoms (“Ce aryl”; e.g., phenyl). In some aspects, an aryl group has 10 ring carbon atoms (“C10 aryl”; e.g., naphthyls such as 1- naphthyl and 2-naphthyl). In some aspects, an aryl group has 14 ring carbon atoms (“C14 aryl”; e.g., anthracyl). “Aryl” also includes ring systems wherein the aryl ring, as defined above, is fused with one or more cycloalkyl or heterocycle groups wherein the radical or point of attachment is on the aryl ring, and in such instances, the number of carbon atoms continues to designate the number of carbon atoms in the aryl ring system. One or more fused cycloalkyl or heterocycle groups can be 4 to 7-member saturated or partially unsaturated cycloalkyl or heterocycle groups. It is understood that when an aryl group is used as a linking group, in a broad sense, it includes arylenes.“Arylalkyl” refers to either an alkyl group as defined herein substituted with an aryl group as defined herein or to an aryl group as defined herein substituted with an alkyl group as defined herein.The term “heterocycle” denotes saturated and partially saturated heteroatom-containing ring radicals wherein there are 1, 2, 3, or 4 heteroatoms independently selected from nitrogen, sulfur, boron, silicon, and oxygen. Heterocyclic rings may comprise monocyclic 3-10 membered rings, as well as 5-16 membered bicyclic ring systems (which can include bridged, fused, and spiro-fused bicyclic ring systems). It does not include rings containing -O-O-, -O- S- or -S-S- portions. Examples of saturated heterocycle groups include saturated 3- to 6- membered heteromonocyclic groups containing 1 to 4 nitrogen atoms [e.g., pyrrolidinyl, imidazolidinyl, piperidinyl, pyrrolinyl, piperazinyl]; saturated 3 to a 6-membered heteromonocyclic group containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms [e.g., morpholinyl]; saturated 3 to 6- membered heteromonocyclic group containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms [e.g., thiazolidinyl]. Examples of partially saturated heterocycle radicals include but are not limited to dihydrothienyl, dihydropyranyl, dihydrofuryl, and dihydrothiazolyl. Examples of partially saturated and saturated heterocycle groups include but are not limited to pyrrolidinyl, imidazolidinyl, piperidinyl, pyrrolinyl, pyrazolidinyl, piperazinyl, morpholinyl, tetrahydropyranyl, thiazolidinyl, dihydrothienyl, 2,3- dihydro-benzo[l,4]dioxanyl, indolinyl, isoindolinyl, dihydrobenzothienyl, dihydrobenzofuryl, isochromanyl, chromanyl, 1,2-dihydroquinolyl, 1,2,3,4-tetrahydro-isoquinolyl, 1, 2,3,4- tetrahydro-quinolyl, 2,3,4,4a,9,9a-hexahydro-lH-3-aza-fluorenyl, 5,6,7-trihydro-l, 2,4- triazolo[3,4-a]isoquinolyl, 3,4-dihydro-2H-benzo[l,4]oxazinyl, benzo[l,4]dioxanyl, 2,3- dihydro-lH-1 X’-benzo[d]isothiazol-6-yl, dihydropyranyl, dihydrofuryl, and dihydrothiazolyl.“Heterocycle” also includes groups wherein the heterocyclic radical is fused / condensed with an aryl or carbocycle radical, wherein the point of attachment is the heterocycle ring. “Heterocycle” also includes groups wherein the heterocyclic radical is substituted with an oxoO group (i.e. ). For example, a partially unsaturated condensed heterocyclic group containing 1 to 5 nitrogen atoms, for example, indoline or isoindoline; a partially unsaturated condensed heterocyclic group containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms; a partially unsaturated condensed heterocyclic group containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms; and a saturated condensed heterocyclic group containing 1 to 2 oxygen or sulfur atoms.The term “fused aromatic rings” refers to systems in which two or more cyclic moieties are joined together by two or more separate covalent bonds. Exemplary fused systems include ortho-fused systems (like naphthalene, etc.) and / ortho- and peri-fused (like phenalene, etc.).The term “heterocycle” also includes “bicyclic heterocycle.” The term “bicyclic heterocycle” denotes a heterocycle as defined herein wherein there is one bridged, fused, or spirocyclic portion of the heterocycle. The bridged, fused, or spirocyclic portion of the heterocycle can be a carbocycle, heterocycle, or aryl group as long as a stable molecule results. Unless excluded by context, the term “heterocycle” includes bicyclic heterocycles. Bicyclic heterocycle includes groups wherein the fused heterocycle is substituted with an oxo group. Non-limiting examples of bicyclic heterocycles include:“Heterocyclealkyl” refers to either an alkyl group as defined herein substituted with a heterocycle group as defined herein or to a heterocycle group as defined herein substituted with an alkyl group as defined herein.The term “heteroaryl” denotes stable aromatic ring systems that contain 1, 2, 3, or 4 heteroatoms independently selected from O, N, and S, wherein the ring nitrogen and sulfur atom(s) are optionally oxidized, and the nitrogen atom(s) are optionally quartemized. Examples include, but are not limited to, unsaturated 5 to 6 membered heteromonocyclyl groups containing 1 to 4 nitrogen atoms, such as pyrrolyl, imidazolyl, pyrazolyl, 2-pyridyl, 3 -pyridyl, 4-pyridyl, pyrimidyl, pyrazinyl, pyridazinyl, triazolyl [e.g., 4H-l,2,4-triazolyl, H4-l,2,3- triazolyl, 2H-l,2,3-triazolyl]; unsaturated 5- to 6-membered heteromonocyclic groups containing an oxygen atom, for example, pyranyl, 2 -furyl, 3 -furyl, etc.; unsaturated 5 to 6- membered heteromonocyclic groups containing a sulfur atom, for example, 2-thienyl, 3- thienyl, etc.; unsaturated 5- to 6-membered heteromonocyclic groups containing 1 to 2 oxygen atoms and 1 to 3 nitrogen atoms, for example, oxazolyl, isoxazolyl, oxadiazolyl [e.g., 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl, 1,2,5-oxadiazolyl]; unsaturated 5 to 6-membered heteromonocyclic groups containing 1 to 2 sulfur atoms and 1 to 3 nitrogen atoms, for example, thiazolyl, thiadi azolyl [e.g., 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl], In certain aspects, the “heteroaryl” group is an 8, 9, or 10-membered bicyclic ring system. Examples of 8, 9, or 10-membered bicyclic heteroaryl groups include benzofurazanyl, benzothiophenyl, benzothiazolyl, benzoxazolyl, quinazolinyl, quinoxalinyl, naphthyridinyl, quinolinyl, isoquinolinyl, benzofuranyl, indolyl, indazolyl, and benzotri azolyl.“Heteroaryl alkyl” refers to either an alkyl group as defined herein substituted with a heteroaryl group as defined herein or to a heteroaryl group as defined herein substituted with an alkyl group as defined herein.As used herein, “carbocyclic,” “carbocycle,” or “cycloalkyl” includes a saturated or partially unsaturated (i.e., not aromatic) group containing all carbon ring atoms and from 3 to 14 ring carbon atoms (“C3-14 cycloalkyl”) and zero heteroatoms in the non-aromatic ring system. In some aspects, a cycloalkyl group has 3 to 10-ring carbon atoms (“C3-10 cycloalkyl”). In some aspects, a cycloalkyl group has 3 to 9 ring carbon atoms (“C3-9 cycloalkyl”). In some aspects, a cycloalkyl group has 3 to 8-ring carbon atoms (“C3-8 cycloalkyl”). In some aspects, a cycloalkyl group has 3 to 7-ring carbon atoms (“C3-7 cycloalkyl”). In some aspects, a cycloalkyl group has 3 to 6-ring carbon atoms (“C3-6 cycloalkyl”). In some aspects, a cycloalkyl group has 4 to 6-ring carbon atoms (“C4-6 cycloalkyl”). In some aspects, a cycloalkyl group has 5 to 6-ring carbon atoms (“C5-6 cycloalkyl”). In some aspects, a cycloalkyl group has 5 to 10 ring carbon atoms (“C5-10 cycloalkyl”). Exemplary C3-6 cycloalkyl groups include, without limitation, cyclopropyl (C3), cyclopropenyl (C3), cyclobutyl (C4), cyclobutenyl (C4), cyclopentyl (Cs), cyclopentenyl (Cs), cyclohexyl (Ce), cyclohexenyl (Ce), cyclohexadienyl (Ce), and the like. Exemplary C3-8 cycloalkyl groups include, without limitation, the aforementioned C3-6 cycloalkyl groups as well as cycloheptyl (C7) and cycloheptenyl (C7), cycloheptadienyl (C7), cycloheptatrienyl (C7), cyclooctyl (Cs), cyclooctenyl (Cs), and the like. Exemplary C3-10 cycloalkyl groups include, without limitation, the aforementioned C3-8 cycloalkyl groups as well as cyclononyl (C9) and cyclononenyl (C9), cyclodecyl (C10), cyclodecenyl (C10), and the like. As the foregoing examples illustrate, in certain aspects, the cycloalkyl group can be saturated or can contain one or more carbon-carbon double bonds. The term “cycloalkyl” also includes ring systems wherein the cycloalkyl ring, as defined above, is fused with one heterocycle, aryl, or heteroaryl ring wherein the point of attachment is on thecycloalkyl ring, and in such instances, the number of carbons continues to designate the number of carbons in the carbocyclic ring system. The term “cycloalkyl” also includes ring systems wherein the cycloalkyl ring, as defined above, has a spirocyclic heterocycle, aryl, or heteroaryl ring wherein the point of attachment is on the cycloalkyl ring, and in such instances, the number of carbons continues to designate the number of carbons in the carbocyclic ring system. The term “cycloalkyl” also includes bicyclic or polycyclic fused, bridged, or spiro ring systems that contain from 5 to 14 carbon atoms and zero heteroatoms in the non-aromatic ring system. Representative examples of “cycloalkyl” include, but are not limited to,The term “bicycle” refers to a ring system wherein two rings are fused together, and each ring is independently selected from carbocycle, heterocycle, aryl, and heteroaryl. Nonlimiting examples of bicycle groups include:The terms “amine” or “amino” as used herein are represented by the formula — NRJR2, where R1and R2can each be substitution groups as described herein, such as hydrogen, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above. “Amido” is — C(O)NR1R2.The term “anhydride” as used herein is represented by the formula Z1C(O)OC(O)Z2, where Z1and Z2, independently, can be an alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.The term “cyclic anhydride,” as used herein, is represented by the formula:where Z1can be an alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.The term “azide,” as used herein, is represented by the formula -N=N=N.The term “aldehyde,” as used herein, is represented by the formula -C(O)H. Throughout this specification, “C(O)” or “CO” is a shorthand notation for C=O, which is also referred to herein as a “carbonyl.”The term “carboxylic acid,” as used herein, is represented by the formula -C(O)OH. A “carboxylate” or “carboxyl” group, as used herein, is represented by the formula -C(O)O'The term “ester” as used herein is represented by the formula -OC(O)R1or -C(O)OR1, where R1can be an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.The term “ether” as used herein is represented by the formula RXOR2, where R1and R2can be, independently, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.The term “epoxy” or “epoxide” as used herein refers to a cyclic ether with a three-atom ring and can be represented by the formula:Z1°Z3Z^^Z4where Z1, Z2, Z3, and Z4can be, independently, H, an alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.The term “ketone” as used herein is represented by the formula R1C(O)R2, where R1and R2can be, independently, an alkyl, halogenated alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.The term “halide,” or “halogen,” or “halo,” as used herein, refers to fluorine, chlorine, bromine, and iodine.The term “hydroxyl,” as used herein, is represented by the formula -OH.The term “nitro,” as used herein, is represented by the formula -NO2.The term “phosphonyl” is used herein to refer to the phospho-oxo group represented by the formula -P(O)(OZJ)2, where Z1can be hydrogen, an alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.The term “silyl” as used herein is represented by the formula -SiZJZ2Z3, where Z1, Z2, and Z3can be, independently, hydrogen, alkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.The term “sulfonyl” or “sulfone” is used herein to refer to the sulfo-oxo group represented by the formula -S(O)2Z1, where Z1can be hydrogen, an alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, or heterocycloalkenyl group described above.The term “sulfide,” as used herein, comprises the formula -S-.As used herein, the term “thio” refers to a group of formulas -SH.As used herein, the term “Cn-Cm alkylthio” refers to a group of formula -S-alkyl, wherein the alkyl group has n to m carbon atoms. In various aspects, the alkyl group has 1 to 6, 1 to 4, or 1 to 3 carbon atoms.As used herein, the term “Cn-Cm alkyl sulfonyl” refers to a group of formula -S(O)- alkyl, wherein the alkyl group has n to m carbon atoms. In various aspects, the alkyl group has 1 to 6, 1 to 4, or 1 to 3 carbon atoms.As used herein, the term “Cn-Cm alkyl sulfonyl” refers to a group of formula -S(O)2- alkyl, wherein the alkyl group has n to m carbon atoms. In various aspects, the alkyl group has 1 to 6, 1 to 4, or 1 to 3 carbon atoms.As used herein, the term “carbamyl” refers to a group of formula -C(0)NH2.As used herein, the term “carbonyl,” employed alone or in combination with other terms, refers to a -C(=O)- group, which may also be written as C(O).As used herein, the term “carboxy” refers to a group of formula -C(O)OH.As used herein, “halogen” refers to F, CI, Br, or I.The term “sulfonylamino” or “sulfonamide,” as used herein, is represented by the formula -S(0)2NH-.“R1,” “R2,” “R3,” “Rn,” etc., where n is some integer, as used herein, can independently possess one or more of the groups listed above. For example, if R1is a straight chain alkyl group, one of the hydrogen atoms of the alkyl group can optionally be substituted with a hydroxyl group, an alkoxy group, an amine group, an alkyl group, a halide, and the like. Depending upon the groups that are selected, a first group can be incorporated within the second group, or alternatively, the first group can be pendant (i.e., attached) to the second group. For example, with the phrase “an alkyl group comprising an amino group,” the amino group can be incorporated within the backbone of the alkyl group. Alternatively, the amino group can be attached to the backbone of the alkyl group. The nature of the group(s) that is (are) selected will determine if the first group is embedded or attached to the second group.Unless stated contrary, a formula with chemical bonds shown only as solid lines and not as wedges or dashed lines contemplates each possible stereoisomer or a mixture of stereoisomer (e.g., each enantiomer, each diastereomer, each meso compound, a racemic mixture, or scalemic mixture).The term “olefinically unsaturated group” or “ethylenically unsaturated group” is employed herein in a broad sense and is intended to encompass any groups containing a carboncarbon double-bonded group (>C=C< group). Exemplary ethylenically unsaturated groups include but are not limited to (meth)acrylate, (meth)acrylamide, (meth)acryloyl, allyl, vinyl, styrenyl, or other >C=C< containing groups.“Polymer” means a material formed by polymerizing one or more monomers and / or one or more oligomers.The term “(co)polymer” includes homopolymers, copolymers, or mixtures thereof.The term “(meth)acryl ...” includes “acryl . . . ,” “methacryl . . . ,” or mixtures thereof.The term “tautomers” refers to two or more isomers of a compound which exist together in equilibrium and are readily interchanged by the migration of an atom or group within the molecule.“Molecular weight” of a polymeric material (including monomeric or macromonomeric materials), as used herein, refers to the number-average molecular weight as measured byJH NMR spectroscopy unless otherwise specifically noted or unless testing conditions indicate otherwise.While aspects of the present invention can be described and claimed in a particular statutory class, such as the system statutory class, this is for convenience only, and one of ordinary skill in the art will understand that each aspect of the present invention can be described and claimed in any statutory class. Unless otherwise expressly stated, it is in no way intended that any method or aspect set forth herein be construed as requiring that its steps be performed in a specific order. Accordingly, where a method claim does not specifically state in the claims or descriptions that the steps are to be limited to a specific order, it is in no way intended that an order be inferred in any respect. This holds for any possible non-express basis for interpretation, including matters of logic with respect to the arrangement of steps or operational flow, plain meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.The present invention may be understood more readily by reference to the following detailed description of various aspects of the invention and the examples included therein and to the Figures and their previous and following description.The present disclosure provides batteries, more specifically zinc-based anode batteries, having a cathodic material as described herein. The described cathodic material undergoes cooperative Zn2+and H+co-insertion in one rate-limiting step, in contrast to sequential Zn2+ / H+co-insertion in conventional OEMs previously reported. This unique mechanism affords a stead discharge plateau, which contrasts with the sloping discharge profile in convention OEMs. Further, the cathodic materials described herein can be readily produced on gram scale from low cost materials, in contrast to previously described OEMs which require multiple synthetic steps, expensive reagents, and which suffer from poor scalability.In one aspect, a battery is provided. In some aspects, in addition, or alternative to any disclosed herein aspects, the battery can comprise a Zn-based anode material. In some aspects, the Zn-based anode material may comprise pure zinc or a zinc allow. In some aspects, the Zn- based anode material may comprise any suitable shape, such as a foil, film, plat, grid, pillar, or the like. In some aspects, the Zn-based anode material may comprise a mixture of pure zinc and / or zinc alloy particles, other electrically conductive particles, and / or one or more binders, for example natural or synthetic rubbers, polysulfones, acrylic polymers, epoxy resins, polystyrene, polytetrafluoroethylene, or the like.In some aspects, in addition, or alternative to any disclosed herein aspects, the batter can comprise a cathode material comprising a compound having a structure of Formula (I) and / or Formula (II):tautomer thereof, whereinR1, R2, R3and R4each is independently selected from C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), or halide, and wherein R1, R2, R3and R4each is independently and optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl- )(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3- 10 heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, the cathode material has the structureor a tautomer thereof.In some aspects, in addition, or alternative to any disclosed herein aspects, R1and R2are independently selected from C1-12 alkyl, C1-12 alkoxy, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Cs-i3 heteroaryl), and halide, each of which is optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl),aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, R1and R2are independently selected from Ci-6 alkyl, Ci-6 alkoxy, Ce-14 aryl, C5-13 heteroaryl, and halide, each of which is optionally substituted with one or more of C1-12 alkyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, R1and R2are each independently C5-13 heteroaryl, each of which is optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, R1and R2are each pyrazolyl, each of which is optionally substituted with one or more of C1-12 alkyl, Ci- 12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, the cathodic material comprises a compound having the structure:In some aspects, in addition, or alternative to any disclosed herein aspects, R1and R2are each independently halide, such as each independently fluoro, chloro, bromo, or iodo.In some aspects, in addition, or alternative to any disclosed herein aspects, the cathodic material comprises a compound having the structure:In some aspects, in addition, or alternative to any disclosed herein aspects, R1and R2are each independently C1-12 alkoxy, each of which is optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, R1and R2are each independently C1-6 alkoxy.In some aspects, in addition, or alternative to any disclosed herein aspects, the cathodic material comprises a compound having the structure:In some aspects, in addition, or alternative to any disclosed herein aspects, R1and R2are each independently Ce-14 aryl, each of which is optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, R1and R2are each independently phenyl, each of which is optionally substituted with one or more of Ci- 12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, R1and R2are each independently unsubstituted phenyl.In some aspects, in addition, or alternative to any disclosed herein aspects, the cathodic material comprises a compound having the structure:In some aspects, in addition, or alternative to any disclosed herein aspects, R1and R2are independently selected from C1-12 alkyl and Ce-14 aryl, each of which is optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, the cathodic material comprises a compound having a structure selected from:In some aspects, in addition, or alternative to any disclosed herein aspects, the cathode material has the structuretautomer thereof.In some aspects, in addition, or alternative to any disclosed herein aspects, R3and R4are independently selected from C1-12 alkyl, C1-12 alkoxy, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Cs-i3 heteroaryl), and halide, each of which is optionally substituted with one or more ofCi-12 alkyl, Ci-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, R3and R4are independently selected from C1-6 alkyl, C1-6 alkoxy, Ce-14 aryl, C5-13 heteroaryl, and halide, each of which is optionally substituted with one or more of C1-12 alkyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, R3and R4are each independently C5-13 heteroaryl, each of which is optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, R3and R4are each pyrazolyl, each of which is optionally substituted with one or more of C1-12 alkyl, Ci- 12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, R3and R4are each independently halide, such as each independently fluoro, chloro, bromo, or iodo.In some aspects, in addition, or alternative to any disclosed herein aspects, R3and R4are each independently C1-12 alkoxy, each of which is optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, R3and R4are each independently Ci-6 alkoxy.In some aspects, in addition, or alternative to any disclosed herein aspects, R3and R4are each independently Ce-14 aryl, each of which is optionally substituted with one or more of Ci-12 alkyl, Ci-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, R3and R4are each independently phenyl, each of which is optionally substituted with one or more of Ci- 12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, R3and R4are each independently unsubstituted phenyl.In some aspects, in addition, or alternative to any disclosed herein aspects, R3and R4are independently selected from C1-12 alkyl and Ce-14 aryl, each of which is optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.In some aspects, in addition, or alternative to any disclosed herein aspects, the cathodic material comprises a compound having the structure:In some aspects, in addition, or alternative to any disclosed herein aspects, the battery further comprises an electrolyte. Any electrolyte suitable for use in batteries may be used. In some aspects, in addition, or alternative to any disclosed herein aspects, the electrolyte is an aqueous electrolyte. In some aspects, in addition, or alternative to any disclosed herein aspects, the electrolyte comprises Zn2+ions, such as but not limited to Zn(OTf)2, ZnSCh, ZnCh, Zn(BF4)2, Zn(C104)2, Zn(acetate)2, Zn(N0s)2, Zn(TFSi)2, ZnBrc, or a combination thereof.In some aspects, in addition, or alternative to any disclosed herein aspects, Zn2+is present in an amount of about 0.005 M to about 4 M, including exemplary values of about 0.005 M, about 0.001 M, about 0.005 M, about 0.01 M, about 0.05 M, about 0.1 M, about 0.2 M, about 0.3 M, about 0.4 M, about 0.5 M, about 0.6 M, about 0.7 M, about 0.8 M, about 0.9M, about 1.0 M, about 1.2 M, about 1.4 M, about 1.6 M, about 1.8 M, about 2.0 M, about 2.2M, about 2.4 M, about 2.6 M, about 2.8 M, about 3.0 M, about 3.2 M, about 3.4 M, about 3.6M, about 3.8 M, about 4.0 M, or any subrange formed from the above exemplary values.In some aspects, in addition, or alternative to any disclosed herein aspects, the electrolyte comprises one or more of tetrabutylammonium perchlorate, ethylenediaminetetraacetic acid, urea, sodium triflate, sodium bisulfate, tartaric acid, succinic acid, citric acid, tetrabutylammonium sulfate, sodium perchlorate, lithium bis(trifluoromethane)sulfonimide, or any combination thereof.In some aspects, in addition, or alternative to any disclosed herein aspects, the electrolyte comprises an amount of an organic solvent. Suitable organic solvents may be readily identified by the skilled person. In some aspects, in addition, or alternative to any disclosed herein aspects, the organic solvent is miscible with an aqueous solution. Representative examples of such organic solvents include, but are not limited to, 1,3 -di oxolane, ethylene glycol, ethanol, glycerol, acetonitrile, dimethyl sulfoxide, dimethyl carbonate, or a combination thereof.In some aspects, in addition, or alternative to any disclosed herein aspects, the battery exhibits a specific capacity of about 100 mAh g'1to about 350 mAh g'1when charged / discharged at 0.2C to 10C, including exemplary values of about 100, about 110, about 120, about 130, about 140, about 150, about 160, about 170, about 180, about 190, about 200, about 210, about 220, about 230, about 240, about 250, about 260, about 270, about 280, about290, about 300, about 310, about 320, about 330, about 340, or about 350 mAh g’1, or any subrange formed from the above exemplary values.In some aspects, in addition, or alternative to any disclosed herein aspects, the battery exhibits a coulombic efficiency of greater than 90 % for at least 500 cycles.In some aspects, in addition, or alternative to any disclosed herein aspects, the battery exhibits a capacity retention greater than about 75% when charged / discharged at 1 C for at least 500 cycles.In some aspects, in addition, or alternative to any disclosed herein aspects, the battery further comprises a separator. Any known in the art suitable for the desired operation separator can be utilized. In some aspects, the separator comprises ceramic or glass particles or fibers embedded in a polymeric matrix of textile fibers; cellulose-based film, polypropylene films, polypropylene / polyethylene films, fluorinated grafted polypropylene / polyethylene films, or a combination thereof.In another aspect, a system is provided. In some aspects, in addition, or alternative to any disclosed herein aspects, the system comprises one or more of the batteries described herein. In some aspects, in addition, or alternative to any disclosed herein aspects, the system is an energy storage system.In another aspect, an article is provided. In some aspects, in addition, or alternative to any disclosed herein aspects, the article comprises one or more of the batteries described herein.In some aspects, in addition, or alternative to any disclosed herein aspects, the article is a vehicle, such as a hybrid electric vehicle or an all-electric vehicle. In some aspects, in addition, or alternative to any disclosed herein aspects, the article comprises an electronic device. In some aspects, in addition, or alternative to any disclosed herein aspects, the article comprises a portable electronic device, a laptop, a watch, or a cell phone. In some aspects, the articles can comprise hand-held and / or wearable electronic devices, such as a phone, watch, or laptop computer; stationary electronic devices, such as a desktop or mainframe computer; an electric tool, such as a power drill; an electric or hybrid land, water, or air-based vehicles, such as a boat, submarine, bus, train, truck, car, motorcycle, moped, powered bicycle, airplane, drone, other flying vehicle, or toy versions thereof; or for other toys. In some aspects, the batteries or systems disclosed herein can be used for energy storage, such as in storing electricpower from wind, solar, wave, hydropower, or nuclear energy and / or in grid storage, or as a stationary power store for small-scale use, such as for a home, business, or hospital.In another aspects, a method is provided of making a battery.In some aspects, in addition, or alternative to any disclosed herein aspects, the method comprises providing a Zn-based anode.In some aspects, in addition, or alternative to any disclosed herein aspects, the method comprises providing a cathode material comprising a compound having a structure of Formula (I) and / or Formula (II), or a tautomer thereof, as described herein.In some aspects, in addition, or alternative to any disclosed herein aspects, the method comprises providing an electrolyte.Additional AspectsIn view of the described compounds, compositions, devices, articles, and methods, hereinbelow are described certain more particular aspects of the disclosure. These particularly recited aspects should not, however, be interpreted to have any limiting effect on any different claims containing different or more general teachings described herein, or that the “particular” aspects are somehow limited in some way other than the inherent meanings of the language and formulae literally used therein.Aspect 1. A battery comprising: a Zn-based anode material; a cathode material comprising a compound having a structure of Formula (I) and / or Formula (II):tautomer thereof, whereinR1, R2, R3and R4each is independently selected from C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), or halide, and wherein R1, R2, R3and R4each is independently and optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl- )(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3- 10 heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.Aspect 2. The battery of aspect 1, wherein the battery further comprises an electrolyte.Aspect 3. The battery of aspect 2, wherein the electrolyte is an aqueous electrolyte.Aspect 4. The battery of any one of aspects 2-3, wherein the electrolyte comprises Zn2+ions.Aspect s. The battery of any one of aspects 2-4, wherein the electrolyte comprises Zn(OTf)2,ZnSO4, ZnCh, Zn(BF4)2, Zn(C104)2, Zn(acetate)2, Zn(N0s)2, Zn(TFSi)2, ZnBrc, or a combination thereof.Aspect 6. The battery of any one of aspects 2-5, wherein Zn2+is present in an amount of about 0.005 M to about 4 M.Aspect 7. The battery of any one of aspects 2-6, wherein the electrolyte comprises one or more of tetrabutyl ammonium perchlorate, ethylenediaminetetraacetic acid, urea, sodium tritiate, sodium bisulfate, tartaric acid, succinic acid, citric acid, tetrabutylammonium sulfate, sodium perchlorate, lithium bis(trifluoromethane)sulfonimide, or any combination thereof.Aspect 8. The battery of any one of aspects 2-7, wherein the electrolyte comprises an amount of an organic solvent.Aspect 9. The battery of aspect 8, wherein the organic solvent is miscible with aqueous solution and is selected from 1,3-dioxolane, ethylene glycol, ethanol, glycerol, acetonitrile, dimethyl sulfoxide, dimethyl carbonate, or a combination thereof.Aspect 10. The battery of any one of aspects 1-9, wherein the cathode material has the structureor a tautomer thereof, wherein R1and R2are as defined in aspect 1.Aspect 11. The battery of aspect 10, wherein R1and R2are independently selected from Ci- 12 alkyl, Ci-12 alkoxy, -(Co-5 alkyl)(Ce-i4 aryl), -(Co-5 alkyl)(Cs-i3 heteroaryl), and halide, each of which is optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.Aspect 12. The battery of aspect 10 or aspect 11, wherein R1and R2are independently selected from C1-6 alkyl, C1-6 alkoxy, Ce-14 aryl, C5-13 heteroaryl, and halide, each of which is optionally substituted with one or more of C1-12 alkyl as allowed by valency.Aspect 13. The battery of any one of aspects 10-12, wherein R1and R2are independently unsubstituted phenyl.Aspect 14. The battery of any one of aspects 1-9, wherein the cathode material comprises:, a tautomer thereof, or a combination thereof.Aspect 15. The battery of any one of aspects 1-14, wherein the cathode material exhibits a 7i-7i stacking.Aspect 16. The battery of any one of aspects 1-15, wherein the battery exhibits a specific capacity of about 100 mAh g'1to about 350 mAh g'1when charged / discharged at 0.2C to 10C.Aspect 17. The battery of any one of aspects 1-16, wherein the battery exhibits a coulombic efficiency of greater than 90 % for at least 500 cycles.Aspect 18. The battery of any one of aspects 1-17, wherein the battery exhibits a capacity retention greater than about 75% when charged / discharged at 1 C for at least 500 cycles.Aspect 19. The battery of any one of aspects 1-18, further comprising a separator.Aspect 20. A system comprising one or more of the batteries of any one of aspects 1-19.Aspect 21. The system of aspect 20, wherein the system is an energy storage system.Aspect 22. An article comprising one or more of the batteries of any one of aspects 1-19.Aspect 23. The article of aspect 22, wherein the article is a vehicle, such as a hybrid electric vehicle or an all-electric vehicle.Aspect 24. The article of aspect 22, wherein the article comprises an electronic device.Aspect 25. The article of aspect 24, wherein the article comprises a portable electronic device, a laptop, a watch, or a cell phone.Aspect 26. A method of making a battery comprising: providing a Zn-based anode; providing a cathode material comprising a compound having a structure of Formula (I) and / or Formula (II):tautomer thereof, whereinR1, R2, R3and R4each is independently selected from C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), or halide, and wherein R1, R2, R3and R4each is independently and optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency; and providing an electrolyte.A number of aspects of the disclosure have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other aspects are within the scope of the following claims.By way of non-limiting illustration, examples of certain aspects of the present disclosure are given below.EXAMPLESThe following examples are set forth below to illustrate the compounds, compositions, articles, devices, and methods claimed herein, along with associated methods and results according to the disclosed subject matter. These examples are not intended to be inclusive of all aspects of the subject matter disclosed herein, but rather to illustrate representative methods and results. These examples are not intended to exclude equivalents and variations of the present disclosure, which are apparent to one skilled in the art.Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in °C or is at ambient temperature, and pressure is at or near atmospheric. There are numerous variations and combinations of reaction conditions, e.g., component concentrations, temperatures, pressures, and other reaction ranges and conditions that can be used to optimize the product purity and yield obtained from the described process. Only reasonable and routine experimentation will be required to optimize such process conditions.Zn-Tetrazine Batteries with Cooperative Zn2+ / H+InsertionThese examples describe the investigation of 1,2,4,5-tetrazine derivatives as low-cost and synthetically modular organic electrode materials in rechargeable aqueous Zn-ion batteries (AZIBs). The substituents at the 3,6-positions of the tetrazine were found to be critical for cycling stability. While heteroatom substituents (chloro, methoxy, pyrazole) lead to the rapid decomposition of electrode materials in the electrolyte, the installation of phenyl groups enhances the cycling stability via 7t-7t stacking. Spectroscopic characterization suggests a cooperative Zn2+and H+insertion mechanism. This unique cooperativity of Zn2+and H+leads to a steady discharge plateau, in contrast to the undesirable sloping voltage profile typically observed in Zn-organic batteries.Aqueous zinc ion batteries (AZIBs) are a class of promising grid-scale energy storage systems due to their inherent safety and low cost. The high theoretical capacity (820 mAh g'1), stability, and low toxicity of zinc metal make it an ideal anode material for AZIBs.[1,2]Conventional cathode materials in AZIBs are based on inorganic metal materials, e.g., manganese oxides,[3]vanadium oxides,[4,5]and Prussian blue analogs.16 8|However, supply chain issues and high costs associated with transition metals limit their adoption into gridscale energy storage. As an alternative, organic electrode materials (OEMs) based on abundant elements, e.g., C, H, N, and S, could overcome these problems.|2-9 11 1Recently reported Zn / quinone batteries1'2 201(FIG. 1A) exhibit comparable performance to state-of-the-art Zn / Mn02 and Zn / VO2 batteries.Due to the structural diversity of organic compounds, a wide range of redox mechanisms have been discovered, including Zn2+insertion, H+insertion, and Zn2+ / H coinsertion.117 241Among them, the most intriguing is Zn2+ / H+coinsertion, as coinsertion of H+with Zn2+generally affords additional specific capacity. However, a disadvantage of Zn2+ / H+coinsertion is that it often leads to discharge profiles with multiple plateaus (FIG. 1 A) because of the distinct electrochemical kinetics of Zn2+vs. H+insertion. A sloping discharge profile means the cell voltage falls progressively throughout the discharge cycle, which is undesirable for energy storage applications.This example describes several 1,2,4,5-tetrazine derivatives, which undergo cooperative Zn2+and H+coinsertion in one step in contrast to stepwise sequential Zn2+ / H+insertion in other OEMs. This unique ion-insertion mechanism affords a steady dischargeplateau (FIG. IB), unlike the sloping discharge profile in conventional OEMs.1'7 I9‘21 241Moreover, 1,2,4,5-tetrazines can be readily produced from gram-scale reactions of low-cost sulfur powder, hydrazine (N2H4), and organic nitriles. This stands in contrast to conventional OEMs, which typically require multiple synthetic steps, expensive reagents, and suffer from poor scalability. Among the six tetrazine derivatives examined (FIG. 2), the best-performing compound 4 (3,6-diphenyl-l,2,4,5-tetrazine) exhibits a specific capacity of 222 mAh g'1at a stable cell 0.78 V in Zn cell, giving rise to a specific energy of 173 Wh kg'1that rivals the performance of start-of-the-art inorganic cathode materials in AZIBs.Results and DiscussionSolution and solid-state cyclic voltammetry studySeveral tetrazines, including 3,6-bis(3,5-dimethylpyrazol-l-yl)-l,2,4,5-tetrazine (1), 3,6-dichloro-l,2,4,5-tetrazine (2), 3,6-dimethoxy-l,2,4,5-tetrazine (3), have been studied as anolytes in non-aqueous redox flow batteries

[0025] and as cathodes in Li-ion batteries.[26,27]Tetrazines typically exhibit a one-electron redox at ca. -0.09 V vs. Zn2+ / Zn (FIG. 3A), rendering it impractical as cathode materials in AZIBs. However, the coordination of Lewis acidic ions, e.g., Sc3+, Fe2+, and Zn2+, to tetrazine has been shown to shift their redox potentials anodically.|28 3()|To investigate the effect of Zn2+ on the redox potential of tetrazines under conditions relevant to AZIBs, we synthesized six derivatives 1-6 (FIG. 2).[27,31 351The cyclic voltammogram (CV) of 4 in acetonitrile (MeCN) with 0.1 M tetrabutylammonium perchlorate (TBACIO4) and 0.01 M zinc triflate (Zn(OTf)2) shows a quasi-reversible redox event at 0.68 V vs. Zn2+ / Zn, representing a remarkable shift of 0.77 V upon Zn2+addition (FIG. 3A). The solid-state CV of 4 in a two-electrode cell with 3 M Zn(OTf)2 as electrolyte shows a quasi- reversible redox process at 0.83 V vs. Zn2+ / Zn (FIG 3B).The redox event at 0.83 V could be attributed to the insertion of either Zn2+or H+due to the acidic nature of the electrolyte (pH 3.5-4.0).

[0036] To discern the insertion of H+vs. Zn2+, we measure the solid-state CV of 4 without Zn2+at the same pH. A distinctly different CV profile was observed (FIG. 3B). In the absence of Zn2+, compound 4 undergoes a two-electron two-proton insertion to form 4-H2 (FIG. 2), a process that has a large voltage hysteresis (FIGs. 24A-24B). In summary, the addition of Zn2+decreases the charge-discharge gap and increases the redox potential; both are desirable outcomes for battery application.Galvanostatic cycling of tetrazine derivatives 1-6The cycling performances of tetrazine derivatives 1-6 were investigated in two- electrode coin cells using Zn metal as the anode and 3 M zinc sulfate (ZnSCh) or Zn(OTf)2 as the electrolyte. The galvanostatic charge-discharge (GCD) cycling experiments were performed at a rate of 1C assuming two-electron redox processes (200 mAg'1for 1, 356 mAg’1for 2, 284 mA g'1for 3, 229 mA g'1for 4, 311 mA g'1for 5, and 288 mA g'1for 6) with a voltage window of 0.4-1.6 V vs. Zn2+ / Zn. Coin cells of compounds 1, 2, and 3 show rapid capacity fading within the first ten cycles (FIGs. 17A-17B, 18A-18B, and 19). The instability of 1-3 was attributed to their high solubility, as coloration of the separator was observed.We sought to reduce the solubility of tetrazine in an aqueous environment by implementing 7t-7t stacking.[17,37’38]The structure of compound 4 in the solid state features extended 7t-7t stacking (FIG. 28), which is expected to prevent dissolution. Indeed, the GCD of Zn-4 cells exhibits a discharge capacity of 222 mAh g’1, corresponding to 96.9% of the theoretical capacity (FIG. 4A). The GCD curve shows a flat discharge plateau at 0.78 V and a charge plateau at 0.86 V with a small voltage hysteresis of only 84 mV (FIG. 4A). Variablerate experiments conducted at 0.2C, 0.5C, 1C, 2C, 5C, and 10C of Zn-4 cells show capacities at 222, 210, 198, 187, 170, and 148 mAh g’1, respectively (FIG. 4B). Long-term cycling of compound 4 at 1C exhibits good stability with ca. 80% capacity retention after 500 cycles (FIG. 4C).A Ragone plot of specific energy and power shows that compound 4 exhibits similar performance to state-of-the-art inorganic cathode materials in AZIBs, e.g., MnCh and V2O5 (FIG. 5). Despite having a slightly lower specific capacity (222 mAh g'1), 4 shows comparable or superior specific energy than state-of-the-art organic AZIB materials, such as HATN (418 mAh g’1, FIG. 5).

[0013] This was attributed to the stable discharge voltage of 4.We also attempted to increase the specific capacity of 4 further by replacing one phenyl with a methyl group in 5 or an ethyl group in 6. However, the removal of the phenyl group in 5 and 6 leads to higher solubility and significantly faster capacity fading (FIGs. 20A-20B, 21 A- 2 IB, and 22).Evidence for Zn2+insertion in 4After demonstrating the cycling performance of 4 in AZIBs, we set out to investigate its redox mechanism that leads to the stable discharge profile. Galvanostatic intermittenttitration technique study showed 4 has a diffusion coefficient of 1.15 x 10’11m2s’1, similar to typical diffusion rates for Zn2+in organic cathodes (FIG. 25).[17,39]X-ray fluorescence spectroscopic (XRF) analysis shows asignificant increase of Zn signal from 0 to 1796 counts / s upondischarge, followed by a significant decrease upon recharge (FIG. 6B). This result, however, must be interpreted with care since the substantial variation in Zn XRF signal can also be attributed to the formation of zinc-hydroxide-based precipitation, such as Znx(OTf)y(OH)2x-y’(H2O)n, upon proton insertion.[7’20’40]To address this ambiguity, we performed scanning electron microscopy (SEM) measurements and energy dispersive X-ray spectroscopy (EDX) for elemental mapping. The discharge product of 4, as marked by N mapping, overlaid with elemental mapping of Zn and F, suggesting that it contains evenly distributed [Zn(OTf)]+ions (FIG. 7). This observation is consistent with the insertion of Zn2+during discharge. Additionally, on the surface of the electrode, wefound distinct flake-like crystals with strong Zn signals that can be attributed to Znx(OTf)y(OH)2x-y«(H2O)n (FIG. 11B).[7’20’40]Evidence for H+insertion in 4After confirming the insertion of Zn2+, we considered if H+insertion was playing a role in the redox of 4. Typically, Zn2+and H+coinsertion results in two-separate plateaus because of the distinct electrochemical kinetics of Zn2+vs. H+insertion.117 24l The stable discharge profile of 4 suggests that Zn2+and H+coinsertion is unlikely.However, to our surprise, we found substantial evidence for H+insertion. First, IR analysis of the discharged cathode powder shows a sharp peak at 3294 cm’1and a broad peak from 3300 to 3650 cm’1(FIG. 6C). The sharp peak was assigned to the N-H stretch from the proton-inserted product. The broad peak was assigned to Znx(OTf)y(OH)2x-y’(H2O)n, a common product of H+insertion due to the local basic environment created by H+insertion.[6]Upon charging, the N-H and O-H vibrations both disappear, and the original IR profile for pristine 4 returns.The formation of Znx(OTf)y(OH)2x-y’(H2O)n is further supported by the powder X-ray diffraction (PXRD) study. PXRD pattern of the inorganic residues matches those reported for Znx(OTf)y(OH)2x-y’(H2O)n (FIG. 6D).140 431The formation of zinc hydroxide precipitate is commonly attributed to H+insertion.117 24l These PXRD features disappear upon charging,suggesting reversible dissolution of Znx(OTf)y(OH)2xy’(H2O)n upon deinsertion of H+. Overall, both IR and PXRD studies confirmed the insertion of H+in 4.Cooperativity of Zn2+and H+insertion in 4Further examination of PXRD data allows us to identify a PXRD pattern unique to the discharge product (FIG. 6D). Importantly, these features do not match that of 4-Hi (FIGs. 10A- 10B), which is the discharge product of 4 under acidic conditions without Zn2+. This intriguing observation indicates that the coinsertion of Zn2+and H+into 4 does not yield distinct H+- insertion and Zn2+-insertion products, in contrast to previous studies.117 241Although we cannot entirely rule out the possibility of a different phase of 4-Hi, the cycling behavior of 4-Hi is drastically different from 4 (FIGs. 24A-24B). This dissimilarity strongly suggests that 4-Hi is not a discharge product of 4 within a Zn electrolyte environment.Taken together, the most likely redox mechanism involves a two-electron one-proton reduction of 4 to 4-Zn-H, which precipitates out as a triflate salt. The increase of pH in the local environment leads to the concurrent formation of Znx(OTf)y(OH)2x-y’(H2O)n (FIG. 8). During charging, Zn2+and H+deinsert to restore the pristine crystalline structure of 4 and decrease the local pH, causing the Znx(OTf)y(OH)2x-y*(H2O)n to redissolve (FIG. 12). This cooperative Zn2+ / H+insertion mechanism is consistent with the single stable discharge plateau observed in the GCD profile, in contrast to conventional Zn2+ / H+coinsertion materials, which often exhibit discharge profiles with multiple plateaus (FIG. 1A) due to the distinct electrochemical kinetics of Zn2+vs. H+insertion.ConclusionsIn summary, we describe the electrochemical performance of low-cost tetrazine derivatives in AZIBs. The substituents on the 3,6-position of the tetrazine have a significant impact on the cycling stability in AZIBs. Installation of phenyl groups in 4 leads to decreased solubility, likely a result of additional 7t-7t stacking interactions. Compound 4 exhibits discharge a capacity of 222 mAh g'1at a steady voltage of 0.78 V, giving rise to a specific energy comparable to the state-of-the-art inorganic cathode materials in AZIBs.Electrochemical and spectroscopic studies reveal a unique redox mechanism of 4 where Zn2+and H+insertion cooperatively in one electrochemical step to generate a single discharge product. This example highlights that cooperative insertion of Zn2+and H+produces a stable discharge plateau, in contrast to the sloping discharge profile typically seen in Zn2+and H+coinsertion materials Cooperative Zn2+ / H+ insertion mechanism could be observed in a broader range of redox-active organic materials in AZIBs,[44,45]and should be considered as a strategy for designing OEMs with stable discharge voltage profiles.References for Experimental Examples[1] M. Song, H. Tan, D. Chao, H. J. Fan, Adv. Fund. Mater. 2018, 28, 1802564.[2] N. Zhang, X. Chen, M. Yu, Z. Niu, F. Cheng, J. Chen, Chem. Soc. 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[0050] N. Zhang, F. Cheng, Y. Liu, Q. Zhao, K. Lei, C. Chen, X. Liu, J. Chen, J. Am. Chem. Soc. 2016, 138, 12894-12901.Supplementary Experimental Details for ExamplesGeneral Experimental DetailsAll experiments were carried out under nitrogen (or argon) atmosphere using an MBraun glovebox and / or standard Schlenk techniques unless stated otherwise. 'H and13C NMR spectra were recorded on Bruker 400 or 600 MHz spectrometer and were externally referenced to the NMR residual solvent peaks. ATR-IR spectra were measured using a Nicolet IR 200 with a diamond ATR accessory. Cyclic voltammetry and potentio-electrochemical impedance spectroscopy experiments were performed with a Biologic SP-150 or SP-50 singlechannel potentiostat. Galvanostatic cycling experiments were performed with a LAND CT2001A battery testing system. X-ray fluorescence (XRF) spectra were measured by anOlympus / Innov-X X-5000 XRF analyzer with a tantalum X-ray tube source and a Silicon Drift Detector. Unless otherwise noted, all solvents were degassed and dried using a Pure Process Technology (PPT) solvent purification system and stored under an atmosphere of nitrogen over 4 A molecular sieves. All glasswares were dried at 175 °C before use. All reagents were purchased from Sigma Aldrich unless otherwise noted.Preparation and Characterization of CompoundsSynthesis and Characterization of Triaminoguanidine Monohydrochloride (la)Triaminoguanidine monohydrochloride was prepared according to a modified literature procedure.[1]Guanidine hydrochloride (5.01 g, 0.0524 mol) was dissolved in 1,4-dioxane (30 mL) under a nitrogen atmosphere. To the reaction mixture while stirring, hydrazine monohydrate (98%, 0.178 mol, 8.64 mL) was added dropwise. The reaction mixture was then refluxed at 103 °C for 2 hours, resulting in a colorless precipitate. The precipitate was collected by filtration and washed with 1,4-dioxane (2 x 10 mL) and dried under vacuum (60 °C) overnight to yield pure product as a colorless fluffy solid (6.9 g, 94%).13C NMR (100 MHz, D2O) 5 159.53. Matching reported literature data.[1]Synthesis and Characterization of 3,6-Bis(3,5-dimethylpyrazol-l-yl)-l,2-dihydro-l,2,4,5- tetrazine (lb)3.6-bis(3,5-dimethylpyrazol-l-yl)-l,2-dihydro-l,2,4,5-tetrazine was prepared according to a modified literature procedure)21Triaminoguanidine monohydrochloride (la, 2.00 g, 14.2 mmol) was dissolved in DI water (15 mL) under a nitrogen atmosphere. To the reaction mixture, acetylacetone (3.00 mL, 28.7 mmol) was added dropwise over 25 minutes while stirring at room temperature. After the dropwise addition was completed, the reaction mixture was stirred at room temperature for 30 minutes followed by heating at 70 °C for four hours to afford a yellow precipitate. The precipitate was collected by filtration, washed with DI water (1,000 mL), and dried in vacuo (60 oC) overnight to afford a bright yellow powder (1.3 g, 68%). literature)21'H NMR (400 MHz, CDCh) 5 8.08 (s, 2H), 5.97 (s, 2H), 2.49 (s, 6H), 2.23 (s, 6H).13C NMR (100 MHz, DMSO-t / 6) 5 149.88, 145.76, 142.17, 109.91, 13.74, 13.43. Matching reported literature data)21Synthesis and Characterization of 3,6-Bis(3,5-dimethylpyrazol-l-yl)-l,2,4,5-tetrazine (1)3.6-Bis(3,5-dimethylpyrazol-l-yl)-l,2,4,5-tetrazine was prepared according to a modified literature procedure)31To a slurry of 3,6-bis(3,5-dimethylpyrazol-l-yl)-l,2-dihydro- 1,2,4,5-tetrazine (lb, 0.500 g, 1.84 mmol) inNMP (2 mL) was added NO2* gas in four portions (4 x 24 mL). The reaction mixture immediately turned a deep red and was allowed to stir open to the atmosphere until all the excess NO2 was removed by the hood exhaust. The mixture was poured into an ice bath (20 mL) and filtered, washing with ice water (2 x 2 mL), and dried in vacuo (60 °C) overnight to afford 1 as a bright red powder (0.39 g, 80%). *Generation of NO2 gas: A24 mL syringe was filled with air (8 mL) and NO gas (16 mL) from a Schlenk line setup. The gas in the syringe immediately turned brown, indicating formation of NO2.‘HNMR (400 MHz, CDCh) 5 6.20 (s, 2H), 2.71 (s, 6H), 2.39 (s, 6H).13C NMR (100 MHz, DMSO-t / 6) 5 159.25, 153.08, 143.59, 111.47, 14.13, 13.93. Matching reported literature data)21Synthesis and Characterization of 3,6-dihydrazinyl-l,2,4,5-tetrazine (2a)3.6-dihydrazinyl-l,2,4,5-tetrazine was prepared according to a modified literature procedure.1413,6-Bis(3,5-dimethylpyrazol-l-yl)-l,2,4,5-tetrazine (1, 769 mg, 2.85 mmol) was dissolved in MeCN (12 mL). Hydrazine hydrate (98%, 0.304 mL, 2.26 mmol) was added dropwise over five minutes while stirring at room temperature. The reaction mixture was refluxed for 30 minutes. The reaction mixture was allowed to cool down to room temperature and the dark red precipitate was collected by filtration. The precipitate was washed with MeCN (6 x 50 mL) and dried overnight at 70 °C to afford 2a as a dark red powdered product (330 mg, 82%).'H NMR (400 MHz, DMSO-t / 6) 5 8.39 (s, 2H), 4.25 (s, 4H). Matching reported literature data.[5]Synthesis and Characterization of 3,6-dichloro-l,2,4,5-tetrazine (2)3.6-dichloro-l,2,4,5-tetrazine was prepared according to a modified literature procedure.[6]3,6-dihydrazinyl-l,2,4,5-tetrazine (2a, 331 mg, 2.33 mmol) was dissolved in MeCN (3.33 mL) and stirred in an ice bath at 0 °C. To the reaction mixture, a solution of trichloroisocyanuric acid (1.14 g, 4.89 mmol) in MeCN (6.6 mL) was added dropwise over one hour. Upon completion of the dropwise addition, the reaction mixture was allowed to warm up to room temperature while stirring for an additional 20 minutes. The colorless precipitate was filtered, and the filtrate was concentrated under nitrogen at room temperature overnight to afford an orange solid. The orange solid was purified via flash chromatography (SiCh, hexanes / dichloromethane 1 : 1) to afford 2 as a bright orange crystalline solid (200 mg, 57%).13C NMR (100 MHz, DMSO-t / 6) 5 167.57. Matching reported literature data.[6]Synthesis and Characterization of 3,6-methoxy-l,2,4,5-tetrazine (3)3,6-dimethoxy-l,2,4,5-tetrazine was prepared according to a modified literature procedure.1613,6-dichloro-l,2,4,5-tetrazine (2, 0.055 g, 0.36 mmol) and sodium methoxide (0.110 g, 2.04 mmol) were dissolved in anhydrous methanol (1 mL). The reaction mixture was allowed to stir at room temperature for 24 hours, and the solution was concentrated under nitrogen to afford a crude red powder. The product was purified via flash chromatography (SiCh, hexanes / EtOAc 90: 10 to afford 3 as orange / pink crystals (41 mg, 80%).1H NMR (400 MHz, CDCh) 5 4.25 (s, 6H).13C NMR (100 MHz, CDCh) 5 166.57, 56.86. Matching reported literature data.[6]Synthesis and Characterization of 3,6-diphenyl-l,2-dihydro-l,2,4,5-tetrazine (4-Hi)4»H24 34%3,6-diphenyl-l,2-dihydro-l,2,4,5-tetrazine was prepared according to a modified literature procedure.[7]Sulfur powder (1.00 g, 3.91 mmol) was dissolved in a solution of EtOH (15 mL) and benzonitrile (5.00 g, 48.5 mmol) under a nitrogen atmosphere at room temperature. The reaction mixture was cooled to 0 °C while stirring. To the reaction mixture, hydrazine monohydrate (80%, 164.9 mmol, 10.00 mL) was added in 1.00 mL portions. The reaction mixture was allowed to stir at room temperature for two hours before being refluxed for two hours. Upon cooling to room temperature, a dark yellow precipitate formed. The precipitate was collected and washed with cold EtOH (0 °C, 2 * 10 mL) and DI water (100 mL). The dark yellow precipitate was used directly in the following oxidation step to generate 4The above reaction generates a mixture of 4-Hi and 4. Minimizing exposure of 4-Hi to oxygen is vital to prevent contamination of 4. To obtain spectroscopic and electrochemical measurements, a second method was utilized to prevent oxidation. All solvents and liquid reagents were sparged with nitrogen for 30 minutes prior to use. 3,6-diphenyl-l,2-dihydro- 1,2,4,5-tetrazine was prepared according to a modified literature procedure)81Benzonitrile (1.00 g, 9.70 mmol) and EtOH (3 mL) was stirred at room temperature under nitrogen. To the reaction mixture, hydrazine monohydrate (98%, 1.41 mL, 29.1 mmol) was added, followed by a solution of 3 M Zn(OTf)2 (0.484 mL, 1.45 mmol). The reaction mixture was stirred at 60 °Cfor 12 hours. The reaction mixture solidified into a yellow solid and was washed via cannula filtration under nitrogen with 1 M HC1 (2 x 50 mL), DI water (2 x 50 mL), hexanes (2 x 50 mL), and diethyl ether (5 mL). The yellow solid was dried under vacuum (60 °C) overnight to afford 4-Hi as a light-yellow solid (99.7 mg, 8.70%). The compound was stored under nitrogen after isolation.'H NMR (400 MHz, CDCh) 5 7.71 - 7.65 (m, 4H), 7.50 - 7.40 (m, 6H), 7.25 (s, 2H).Synthesis and Characterization of 3,6-diphenyl-l,2,4,5-tetrazine (4)3,6-diphenyl-l,2,4,5-tetrazine was prepared according to a modified literature procedure. 3,6-diphenyl-l,2-dihydro-l,2,4,5-tetrazine (4-Hi) was used directly from the bulk synthesis.[7]The dark yellow precipitate was suspended in an aqueous sodium nitrite solution (1.76 g, 146 mmol) while stirring at room temperature. To the suspension, 1 M AcOH was added dropwise until the pH of the solution was around 3. After the addition was completed, the reaction was allowed to stir at room temperature for 2 hours to afford a purple / red precipitate. The precipitate was collected by filtration and washed with water (10 mL) and MeOH (1 mL). The resulting solid was purified via flash chromatography (SiCh, hexanes / EtOAc 90: 10) to afford a purple solid. The solid was recrystallized by dissolving in boiling ethanol and cooling to -20 C overnight to afford purple needles (1.9 g, 34% yield over two steps).‘HNMR (400 MHz, CDCh) 5 8.69 - 8.63 (m, 4H), 7.66 - 7.60 (m, 6H).13C NMR (100 MHz, CDCh) 5 163.99, 132.70, 131.80, 129.33, 128.00. Matching reported literature data.[7]Synthesis and Characterization of 3-methyl-6-phenyl-l,2,4,5-tetrazine (5)S 31 %3-methyl-6-phenyl-l,2,4,5-tetrazine was prepared according to a previously established literature procedure.[9]Under a nitrogen atmosphere, acetonitrile (5.00 mL, 95.7 mmol) and hydrazine monohydrate (9.61 mL, 197 mmol) was allowed to stir at 70 °C for 30 minutes. A second solution containing benzonitrile (0.600 g, 5.82 mmol) and 2 M Zn(C104)2 (0.582 mL, 1.16 mmol) was added to the first solution. The second solution was quantitatively transferred with acetonitrile (3 x 0.56 mL) for a total of 6.69 mL of acetonitrile (128 mmol) used in the reaction. The reaction mixture was stirred at 70 °C for 14 hours. The reaction mixture was exposed to air at 70 °C while stirring to allow the 3,6-dimethyl-l,2,4,5-tetrazine byproduct to form and allowed to stir for 30 minutes. The reaction mixture was concentrateddown with nitrogen at 70 °C to remove the excess hydrazine and byproduct. After drying, the crude was rinsed with DI water (3 x 10 mL) and dried at 60 °C.The remaining solid crude is a mixture of 4, 4-Hi, 3-methyl-6-phenyl-l,4-dihydro- 1,2,4,5-tetrazine, and 5. The solid is immediately used in the following oxidation step without further purification or isolation. The crude solid was suspended in an aqueous sodium nitrite solution (6.00 g, 70.6 mmol). To the suspension, 1 M HC1 was added dropwise until the pH of the solution was around 3. After the addition was completed, the reaction was allowed to stir at room temperature for 2 hours to afford a purple / red precipitate. The precipitate was collected by filtration and washed with DI water (10 mL). The resulting solid was purified via flash chromatography (SiCh, hexanes then hexanes / EtOAc 95:5) to afford a deep purple crystallinelike compound (310 mg, 31% yield).'H NMR (400 MHz, CDCh) 5 8.63 - 8.49 (m, 2H), 7.64 - 7.52 (m, 3H), 3.08 (s, 3H).13C NMR (100 MHz, CDCh) 5 167.26, 164.10, 132.54, 131.79, 129.23, 127.91, 21.16. Matching reported literature data. [9]Synthesis and Characterization of 3-ethyl-6-phenyl-l,2,4,5-tetrazine (6)3-ethyl-6-phenyl-l,2,4,5-tetrazine was prepared according to a previously established literature procedure.[9]Under a nitrogen atmosphere, propionitrile (5.00 mL, 71.9 mmol) and hydrazine monohydrate (7.78 mL, 160 mmol) was allowed to stir at 70 °C for 30 minutes. A second solution containing benzonitrile (0.500 g, 4.85 mmol) and 2 M Zn(C104)2 (0.484 mL, 0.970 mmol) was added to the first solution. The second solution was quantitatively transferred with propionitrile (3 x 0.800 mL) for a total of 7.2 mL of propionitrile (103 mmol) used in the reaction. The reaction mixture was stirred at 70 °C for 14 hours. The reaction mixture was concentrated down with nitrogen at 70 °C. After drying, the crude was rinsed with DI water (3 x 10 mL) and dried at 60 °C.The remaining solid crude was immediately used in the following oxidation step without further purification or isolation. The crude solid was suspended in an aqueous sodium nitrite solution (6.00 g, 70.6 mmol). To the suspension, 1 M HC1 was added dropwise until the pH of the solution was around 3. After the addition was completed, the reaction was allowed to stir at room temperature for 2 hours. The reaction mixture was extracted with ethyl acetate and dried down to afford a viscous red oil. The oil was purified via flash chromatography (SiCh, hexanes / EtOAc 90: 1 to hexanes / EtOAc 4: 1) to afford a dark red oil. After drying overnight under vacuum at room temperature and freezing (-20 °C) the oil, the red oil solidified into a red solid (377 mg, 42% yield).'HNMR (400 MHz, CDC13) 5 8.63 - 8.49 (m, 2H), 7.64 - 7.52 (m, 3H), 3.08 (s, 3H).13C NMR (100 MHz, CDCh) 5 167.26, 164.10, 132.54, 131.79, 129.23, 127.91, 21.16. Matching reported literature data.[9]XRD MeasurementsPowder X-Ray DiffractionPowder diffraction data of 4 and 4-Hi were collected using a Bruker D8 Powder X-Ray Diffractometer employing Cu K(a) 1 line with a wavelength of 0.4579 A, step size 0.02°, exposure time of 1 sec per step.Scanning electron microscope (SEM) and energy-dispersive X-ray (EDX)The surface morphology of 4 was characterized using a scanning electron microscope (SEM, Apreo II, Thermo Scientific Co., Ltd, USA). To analyze the discharged state of 4, theelectrode used for SEM analysis was prepared without a binder to eliminate any potential interference from the binder material.X-ray Fluorescence MeasurementsX-ray fluorescence spectra were obtained from 10 mg samples of 4 (pristine, charged, 50% discharge, and 100% discharged). A tantalum anode at 35 keV with a 26 p A tube was utilized for 15 seconds for each sample; the samples were uniformly distributed in a 2” x 2” plastic bag.Infrared SpectroscopyATR-IR spectroscopy spectra were measured under an inert atmosphere using a Nicol et IR 200 with a diamond ATR accessory.Electrochemical MeasurementsTwo-Electrode Solid State Cyclic VoltammetrySolid-state CV experiments were carried out using a two-electrode coin-type cell, consisting of a cathode of 1 or 2 and Zn metal as the anode (see Coin Cell Assembly). The coin cells were allowed to rest for one hour and then subject to a single galvanostatic chargedischarge cycle at 0.5C to ensure consistency between cells. Subsequent CV scans were performed at a scan rate of 0.1 mV s-1.Battery TestingElectrode Powder FabricationCathode powders were prepared utilizing a 5:4: 1 mixture of active material, conductive carbon (Ketjen black), and PTFE (10% aqueous solution of polytetrafluoroethylene) binder. The active material was dissolved in DCM (2 mL). To the solution, Ketjen black was added, and the suspension was sonicated for 30 minutes. The suspension was dried in air at 50 °C followed by vacuum drying for 8 hours. The resulting powder was added to a PTFE solution and milled until a paste-like consistency was obtained. The paste was transferred to a glass substrate and pressed to provide free-standing electrodes. Upon drying at 80 °C overnight, the electrodes were hole punched (<j> 10) to obtain a uniform circular-shaped electrode. The loading level of electroactive material is controlled by 1.0-1.5 mg cm'2.Coin Cell AssemblyCoin-type cells were assembled in open air with powder mixtures of 1, 2, 3, 4, and 5 as the cathode, 3 M ZnSCh or 3 M Zn(OTf)2 as the aqueous electrolyte, GF / D glass microfiber filter paper as the separator, and polished Zn foil as the anode. Coin cells were assembled from bottom to top: coin cell bottom, polished Zn anode, 50 pL electrolyte, separator, 50 pL electrolyte cathode on a stainless steel current collector, wave / conical washer, coin cell top with gasket. Coin cells were crimped in a Gelon GN-CCM20 coin cell crimper at 900 psi and used for battery testing after a rest period of one hour.The zinc metal anode was templated with a hole punch and cut into circular anodes with copper scissors. Prior to assembling each coin cell, the resulting anodes were polished on both sides with sandpaper (grit 1000) and water until a mirror finish was present. The anodes were used directly after polishing.Galvanostatic Charge-Discharge CyclingGalvanostatic charge-discharge cycling was performed with coin-type cells containing 1, 2, 3, 4, 4-Hi, and 5 cathodes with a voltage window of 0.4- 1.6 V ( s. Zn2+ / Zn). The current applied during battery cycling experiments was calculated based on the theoretical capacity of each compound, assuming a two-electron input and the weight of the active cathode material used in each cell.Galvanostatic intermittent titration technique (GITT) experiment of Zn-4The ion diffusion coefficient was determined by GITT analysis utilizing the following equation:Where T (3600 s) is the duration of the current pulse, L is the thickness of the electrode, AESis the steady-state voltage change, and AEi is the voltage change during constant current pulse.Solution phase cyclic voltammetry (CV)Solution phase (CV) experiments were carried out using a three-electrode cell, consisting of a glassy carbon working electrode (0.07 cm2, CH Instruments), a Ag+ / Ag reference electrode (CH Instruments) with 0.01 M AgNCh in MeCN, and a platinum wirecounter electrode (7.5 cm, BASi). Solution CV experiments were performed at 5 mM concentrations under a nitrogen atmosphere.Coin Cell DisassemblyThe cycled coin cells were opened in air after completion of galvanostatic cycling and disassembled with a Gelon GN-CCM20 coin cell crimping machine via a disassembly die set. To prepare the cathodes for post-mortem analysis, they were washed with DI water (3 x 10 mL) and dried at 80 °C under vacuum for 24 hours before being used. Photos were taken after the washing of the electrodes and separators prior to drying.References for Supplementary Experimental Details for Examples[1] K. Rajalakshmi, T. Deng, S. Muthusamy, M. Xie, J. Xie, K. B. Lee, Y. Xu, Spectrochim. Acta - Part A Mol. Biomol. Spectrosc. 2022, 268, 120622.[2] D. Nhu, S. Duffy, V. M. Avery, A. Hughes, J. B. Baell, Bioorganic Med. Chem. Lett. 2010, 20, 4496-4498.[3] M. Coburn, G. Buntain, A. Harris, K. Lee, D. Ott, J. Heterocycl. Chem. 1991, 28, 2049- 2050.[4] D. Chavez, M. Hiskey, J. Heterocycl. Chem. 1998, 35, 1329-1332.[5] D. Chen, H. Yang, Z. Yi, H. Xiong, L. Zhang, S. Zhu, G. Cheng, Angew. Chemie - Int. Ed. 2018, 57, 2081-2084.[6] D. J. Min, F. Miomandre, P. Audebert, J. E. Kwon, S. Y. Park, ChemSusChem 2019, 12, 503-510.[7] M. J. Haddadin, E. H. G. Zadeh, Tetrahedron Lett. 2010, 51, 1654-1656.[8] S. P. J. T. Bachollet, V. Vece, A. N. Mccracken, B. T. Finicle, E. Selwan, N. Ben Romdhane, A. Dahal, C. Ramirez, A. L. Edinger, S. Hanessian, ACS Med. Chem. Lett. 2020, 11, 686-690.[9] S. E. Suh, S. A. Barros, D. M. Chenoweth, Chem. Sci. 2015, 6, 5128-5132.The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalentare intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative compositions and method steps disclosed herein are specifically described, other combinations of the compositions and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein; however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated.

Claims

WHAT IS CLAIMED IS:

1. A battery comprising: a Zn-based anode material; a cathode material comprising a compound having a structure of Formula (I) and / or Formula (II):tautomer thereof, whereinR1, R2, R3and R4each is independently selected from C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), or halide, and wherein R1, R2, R3and R4each is independently and optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.

2. The battery of claim 1, wherein the battery further comprises an electrolyte.

3. The battery of claim 2, wherein the electrolyte is an aqueous electrolyte.

4. The battery of any one of claims 2-3, wherein the electrolyte comprises Zn2+ions.

5. The battery of any one of claims 2-4, wherein the electrolyte comprises Zn(OTf)2,ZnSO4, ZnCh, Zn(BF4)2, Zn(C104)2, Zn(acetate)2, Zn(NOs)2, Zn(TFSi)2, ZnBn, or a combination thereof.

6. The battery of any one of claims 2-5, wherein Zn2+is present in an amount of about 0.005 M to about 4 M.

7. The battery of any one of claims 2-6, wherein the electrolyte comprises one or more of tetrabutylammonium perchlorate, ethylenediaminetetraacetic acid, urea, sodium tritiate, sodium bisulfate, tartaric acid, succinic acid, citric acid, tetrabutylammonium sulfate, sodium perchlorate, lithium bis(trifluoromethane)sulfonimide, or any combination thereof.

8. The battery of any one of claims of 2-7, wherein the electrolyte comprises an amount of an organic solvent.

9. The battery of claim 8, wherein the organic solvent is miscible with aqueous solution and is selected from 1,3-dioxolane, ethylene glycol, ethanol, glycerol, acetonitrile, dimethyl sulfoxide, dimethyl carbonate, or a combination thereof.

10. The battery of any one of claims 1-9, wherein the cathode material has the structureor a tautomer thereof, wherein R1and R2are as defined in claim 1.

11. The battery of claim 10, wherein R1and R2are independently selected from C1-12 alkyl, C1-12 alkoxy, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Cs-i3 heteroaryl), and halide, each of which is optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3- 10 cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3- 10 cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl as allowed by valency.

12. The battery of claim 10 or claim 11, wherein R1and R2are independently selected from C1-6 alkyl, C1-6 alkoxy, Ce-14 aryl, C5-13 heteroaryl, and halide, each of which is optionally substituted with one or more of C1-12 alkyl as allowed by valency.

13. The battery of any one of claims 10-12, wherein R1and R2are independently unsubstituted phenyl.

14. The battery of any one of claims 1-9, wherein the cathode material comprises:, a tautomer thereof, or a combination thereof.

15. The battery of any one of claims 1-14, wherein the cathode material exhibits a 7t-7t stacking.

16. The battery of any one of claims 1-15, wherein the battery exhibits a specific capacity of about 100 mAh g'1to about 350 mAh g'1when charged / discharged at 0.2C to 10C.

17. The battery of any one of claims 1-16, wherein the battery exhibits a coulombic efficiency of greater than 90 % for at least 500 cycles.

18. The battery of any one of claims 1-17, wherein the battery exhibits a capacity retention greater than about 75% when charged / discharged at 1 C for at least 500 cycles.

19. The battery of any one of claims 1-18, further comprising a separator.

20. A system comprising one or more of the batteries of any one of claims 1-19.

21. The system of claim 20, wherein the system is an energy storage system.

22. An article comprising one or more of the batteries of any one of claims 1-19.

23. The article of claim 22, wherein the article is a vehicle, such as a hybrid electric vehicle or an all-electric vehicle.

24. The article of claim 22, wherein the article comprises an electronic device.

25. The article of claim 24, wherein the article comprises a portable electronic device, a laptop, a watch, or a cell phone.

26. A method of making a battery comprising: providing a Zn-based anode; providing a cathode material comprising a compound having a structure of Formula (I) and / or Formula (II):tautomer thereof, whereinR1, R2, R3and R4each is independently selected from C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), or halide, and wherein R1, R2, R3and R4each is independently and optionally substituted with one or more of C1-12 alkyl, C1-12 alkoxy, C1-12 heteroalkyl, -(C0-5 alkyl)(Ce-i4 aryl), -(C0-5 alkyl)(Ci-i3 heteroaryl), -(C0-5 alkyl)(Ce-i4 aryloxy), -(C0-5 alkyl)(C3-io cycloalkyl), -(C0-5 alkyl)(C3-io heterocycloalkyl), -(C0-5 alkyl)(C3-io cycloalkenyl), -(C0-5 alkyl)(C3-io heterocycloalkenyl), aldehyde, amino, carbonyl, ester, ketone, ether, halide, carboxyl, hydroxy, nitro, sulfo-oxo, sulfonyl, sulfone, sulfoxide, thiol, or phosphonyl; and providing an electrolyte.

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