Condensed aromatic molecules as electrode materials

Abstract

Compositions comprising fused aromatic systems, and associated electrodes, electrochemical cells, and charge storage devices are generally described. Preferably, the aromatic system comprises a bis-tetraamino-benzoquinone molecule, and / or a tautomer, oligomer, and / or polymer thereof. Alternatively, the aromatic composition comprises an active material comprising a fused aromatic system comprising carbon atoms, hydrogen atoms, and multiple heteroatoms each replacing a carbon atom. The subject matter of the present invention involves, in some cases, interrelated products, alternative solutions to a particular problem, and / or multiple different uses of one or more systems and / or articles.

Description

[Technical Field]

[0001] Related applications This application claims priority to U.S. Provisional Application No. 63 / 234,849, filed on 19 August 2021, titled "FUSED AROMATIC MOLECULES AS ELECTRODE MATERIALS," which is incorporated whole in this application by reference for all purposes.

[0002] Technical field Compositions containing condensed aromatic systems, as well as related electrodes, electrochemical cells, and charge storage devices, are generally described. [Background technology]

[0003] background Supercapacitors (SCs) are energy storage devices that offer higher power density and longer-term cycle stability compared to lithium-ion batteries (LIBs). However, the energy density of a typical SC using porous carbon as the electrode material is at least two orders of magnitude lower than that of LIBs. Bridging this energy density gap while maintaining the high power of SCs is a challenge toward creating an ideal storage device. One strategy to bridge the energy density gap is to use pseudocapacitive electrode materials. Inorganic oxides, for example, can release charge storage (approximately 160 mAh / g) comparable to batteries through rapid Faraday action while functioning on faster timescales of seconds. However, the best-performing inorganic oxides (e.g., hydrated noble metal oxides such as RuO2·xH2O and IrO2·xH2O) are very expensive for commercial applications of SCs. [Overview of the project] [Means for solving the problem]

[0004] overview Compositions comprising condensed aromatic systems, as well as related electrodes, electrochemical cells, and charge storage devices, are generally described. The subject matter of the present invention may, in some cases, involve interrelated products, alternative solutions to specific problems, and / or multiple different uses of one or more systems and / or articles.

[0005] According to several embodiments, a composition is described, and the composition has the following structure: [ka] This includes the bis-tetraamino-benzoquinone molecule, and / or its tautomers, oligomers, and / or polymers.

[0006] According to one embodiment, an electrode is described, and the electrode has the following structure: [ka] This includes the bis-tetraamino-benzoquinone molecule, and / or its tautomers, oligomers, and / or polymers.

[0007] According to some embodiments, an electrochemical cell is described, the electrochemical cell comprising a first electrode, a second electrode, and an electrolyte, wherein the first electrode and / or the second electrode have a structure such as the one described above, for example, the following: [ka] The electrode comprises a bis-tetraamino-benzoquinone molecule, and / or its tautomers, oligomers, and / or polymers.

[0008] According to one embodiment, an electrochemically active charge storage material is described, which comprises an active material comprising a condensed aromatic system comprising a carbon atom, a hydrogen atom, and a plurality of heteroatoms each replacing a carbon atom, wherein the ratio of carbon atoms to heteroatoms is greater than 1 and less than 2, and the plurality of heteroatoms include N, O, S, and / or Se.

[0009] According to some embodiments, electrochemically active charge storage materials are described, which comprise an active material comprising a condensed aromatic system comprising carbon atoms, hydrogen atoms, and a plurality of heteroatoms each substituting for a carbon atom, at least a portion of the condensed aromatic system being in a planar and / or two-dimensional structure via several hydrogen bonding interactions, wherein the number of hydrogen bonding interactions is greater than or equal to 0.3 and less than or equal to 1 per mole of carbon atoms.

[0010] According to one embodiment, a charge storage device is described, which comprises an electrochemically active charge storage material comprising an active material comprising a condensed aromatic system comprising carbon, hydrogen, and one or more heteroatoms replacing carbon atoms, wherein the electrochemically active charge storage material has a charge capacity greater than or equal to 100 mAh per gram of active material, and / or the electrochemically active charge storage material has a charge capacity greater than or equal to 50 mAh per gram of electrochemically active charge storage material.

[0011] According to some embodiments, a charge storage device is described, which comprises an electrochemically active charge storage material comprising an active material comprising a condensed aromatic system comprising carbon, hydrogen, and one or more heteroatoms replacing carbon atoms, wherein the electrochemically active charge storage material is placed in an electrolyte, and the electrochemically active charge storage material has a charge capacity that is at least 50% greater when the pH of the electrolyte is greater than 2 and less than 12 compared to when the pH of the electrolyte is greater than 2 and less than 12, or greater than 12 and less than 15.

[0012] According to one embodiment, a charge storage device is described, the charge storage device comprising an electrochemically active charge storage material comprising an active material comprising a condensed aromatic system comprising carbon, hydrogen, and one or more heteroatoms replacing carbon atoms, the electrochemically active charge storage material comprising 2.0V vs. Li + At a voltage higher than that of the Li standard reference electrode, it releases at least 90% of its charge capacitance.

[0013] According to some embodiments, a charge storage device is described, which comprises an electrochemically active charge storage material comprising an active material comprising a condensed aromatic system comprising carbon atoms, hydrogen atoms, and a plurality of heteroatoms replacing the carbon atoms, wherein the molar ratio of electrons stored as charge per mole of heteroatoms is greater than or equal to 0.3 and less than or equal to 0.6.

[0014] According to one embodiment, a charge storage device is described, comprising an electrochemically active charge storage material comprising an active material, wherein the active material comprises an organic material, the active material having a solubility of less than or equal to 1 millimoles per liter of solvent at ambient temperature and atmospheric pressure, and the electrochemically active charge storage material having a charge capacity retention rate of greater than or equal to 85% after at least 20,000 cycles.

[0015] Other advantages and novel features of the present invention will become apparent from the following detailed description of various non-limiting embodiments of the invention, when considered in conjunction with the accompanying drawings. If this specification and any document incorporated by reference contain conflicting and / or inconsistent disclosures, this specification shall prevail. If two or more documents incorporated by reference contain conflicting and / or inconsistent disclosures with respect to one another, the document with the later effective date shall prevail.

[0016] Brief explanation of the drawing Non-limiting embodiments of the present invention are described schematically and illustratively with reference to accompanying drawings, which are not intended to be written in any particular proportion. In the drawings, each of the identical or substantially identical components shown is usually represented by only one number. For clarity, not all components are shown in all drawings, or not all components of each embodiment of the present invention are shown where drawings are not necessary for a person skilled in the art to understand the present invention. [Brief explanation of the drawing]

[0017] [Figure 1] Figure 1 shows a schematic diagram of an electrode according to one embodiment.

[0018] [Figure 2] Figure 2 shows a schematic diagram of an electrochemical cell according to one embodiment.

[0019] [Figure 3] Figure 3 shows a schematic diagram of a charge storage device according to one embodiment.

[0020] [Figure 4] Figure 4 shows the synthesis of bis-tetraamino-benzoquinone (BTABQ) and its polymer (pBTABQ) according to one embodiment.

[0021] [Figure 5] Figure 5 shows a schematic diagram of condensed aromatic molecular crystals and their conversion to conjugated ladder oligomers by self-condensation according to one embodiment.

[0022] [Figure 6] Figure 6 shows a schematic diagram of the pseudocapacitive intercalation of various cations into a condensed aromatic material according to one embodiment.

[0023] [Figure 7]Figure 7 shows the three-dimensional (3D) reciprocal lattice of a BTABQ with a maximum resolution of 0.625 Å according to one embodiment, and the inset shows a scanning electron microscope (SEM) image of a BTABQ rod (scale bar: 2 μm).

[0024] [Figure 8] Figure 8 shows a schematic diagram of a two-dimensional (2D) layer of BTABQ molecules formed by hydrogen bonding interactions according to one embodiment.

[0025] [Figure 9] Figure 9 shows a schematic diagram of π-π stacking of a 2D layer of BTABQ according to one embodiment.

[0026] [Figure 10] Figure 10 shows a schematic diagram of the donor-receptor sequence in the 2D layer of BTABQ according to one embodiment.

[0027] [Figure 11] Figure 11 shows the diffuse reflectance ultraviolet-visible near-infrared (DRUV-Vis-NIR) spectra of BTABQ and pBTABQ according to one embodiment.

[0028] [Figure 12] Figure 12 shows cyclic voltammograms (CVs) of BTABQ and pBTABQ obtained at a scanning rate of 10 mVs⁻¹ using a 1 M LiCl aqueous electrolyte according to one embodiment.

[0029] [Figure 13] Figure 13 shows a plot of capacity retention as a function of CV cycle number for BTABQ and pBTABQ according to one embodiment, and the inset shows weight-to-weight capacity as a function of scan speed.

[0030] [Figure 14] Figure 14 shows the electrochemical impedance spectra of BTABQ and pBTABQ according to one embodiment.

[0031] [Figure 15] Figure 15 shows the in situ wide-angle X-ray scattering (WAXS) patterns of an initial and negatively polarized BTABQ according to one embodiment.

[0032] [Figure 16] Figure 16 shows the excitatory energy dispersion (EDS) mapping of pBTABQ according to one embodiment.

[0033] [Figure 17] Figure 17 shows the CV of pBTABQ recorded in an electrolyte containing 1 M NaClO4 in a mixture of water and acetonitrile according to one embodiment.

[0034] [Figure 18] Figure 18 shows a schematic diagram of cation-assisted pseudocapacitive intercalation to BTABQ according to one embodiment.

[0035] [Figure 19] Figure 19 shows the CV obtained at a scanning rate of 5 mVs-1 in several 1 M NaCl electrolytes adjusted to pH values ​​in the range of 0 to 14.7 according to one embodiment.

[0036] [Figure 20] Figure 20 shows a plot of the peak current as a function of the scanning speed according to one embodiment.

[0037] [Figure 21] Figure 21 shows a plot of the weight-specific volume as a function of electrolyte pH obtained from CV at a scanning speed of 0.2 mVs-1 according to one embodiment.

[0038] [Figure 22] Figure 22 shows the excitatory high-resolution O1s and N1s X-ray photoelectron spectra of a polarization electrode according to one embodiment.

[0039] [Figure 23] Figure 23 shows the EDS mapping of a polarized pBTABQ at pH 0 according to one embodiment.

[0040] [Figure 24] Figure 24 shows the EDS mapping of a polarized pBTABQ at pH 14.7 according to one embodiment.

[0041] [Figure 25] Figure 25 shows the DRUV-Vis spectra of initial and immersed pBTABQ in 4M HCl and 6M KOH according to one embodiment.

[0042] [Figure 26] Figure 26 shows the CV of pBTABQ obtained at scan rates of 10, 20, and 40 mVs⁻¹ using a water-in-salt electrolyte (WiSE) of 17 moles of NaClO₄ according to one embodiment.

[0043] [Figure 27] Figure 27 shows the power performance of pBTABQ in WiSE obtained from CV at scanning speeds ranging from 0.2 to 100 mVs-1 on electrodes with active material fillings of 1.5, 2.5, 3.5, and 6 mg cm-2 according to one embodiment.

[0044] [Figure 28] Figure 28 shows a comparison of rate performance for a pBTABQ and associated state-of-the-art LIC cathodes and pseudocapacitive electrodes according to one embodiment.

[0045] [Figure 29] Figure 29 shows a schematic diagram of the four-electron reduction of BTABQ according to one embodiment.

[0046] [Figure 30] Figure 30 shows a schematic diagram of the 12-electron reduction of pBTABQ according to one embodiment. [Modes for carrying out the invention]

[0047] Detailed explanation The increasing demands for electrification of the transportation sector and decarbonization of the grid necessitate the development of electrochemical energy storage (EES) systems that can meet diverse energy and power requirements. Conventional lithium-ion batteries (LICs) and electrochemical capacitors (ECs), as state-of-the-art EES devices, typically provide either high energy or high power. Several attempts have aimed to achieve high power and energy density in hybrid energy storage systems (HESSes) by integrating LICs and ECs at the device level. This approach represents a modular approach to supplying high energy and power to applications where power requirements vary over time, or where the potential for energy recovery at high power is as important as power release. However, the complexity and cost associated with such device integration make their use in package-sensitive applications, such as electric vehicles, impossible. We understand the strong interest in developing materials that combine the high charge capacity of LICs with the fast charging and long cycle life of ECs in a single EES device.

[0048] Electrode materials with abundant redox active sites can be suitable as high-capacitance and high-power materials because the redox sites rapidly transport electrical and ionic charges across the electrode bulk. The charge storage mechanism typically known as such for pseudocapacitance has been identified primarily with short charge diffusion lengths in thin films of redox active transition metal oxides, nitrides, and carbides. However, thick electrode films of these materials with actually relevant mass loading exhibit suboptimal performance due to poor bulk ion and electron transport. Furthermore, the complex roles of interfacial chemistry, crystallinity, and hydration in the electrochemical behavior of conventional inorganic materials limit precise design control, instead requiring composite material synthesis and nanoengineering.

[0049] In contrast to the conventional inorganic materials described above, organic materials offer great structural selectivity and synthetic feasibility for various designs of electrode materials utilizing the Earth's abundant elements. However, conventional organic molecules exhibit inferior electrochemical performance compared to their inorganic counterparts due to their inferior intrinsic conductivity, limited electron delocalization, and high solubility in electrolytes. While strategies such as polymerizing and synthesizing organic molecules using insoluble substrates can limit electrode decomposition, there is a strong desire for molecular designs that simultaneously improve charge transport and accumulation in insoluble organic solids.

[0050] The inventors have realized and recognized that condensed aromatic materials, such as bis-tetraaminobenzoquinone (BTABQ), and its oligomers and / or polymers, can be used as electrode active materials and are suitable for EES. Condensed aromatic materials have a high density of redox active sites in an aromatic skeleton with extended conjugation. In some embodiments, for example, the carbon-to-heteroatom (e.g., N,O) ratio of the material is less than 1.3. The material forms an insoluble solid in both organic and aqueous media via strong intermolecular hydrogen bonding and donor-acceptor π-π interactions. Condensed aromatic materials, such as BTABQ, and its oligomers and / or polymers, exhibit excellent charge storage capacity at high charge-discharge rates in various electrolytes, firstly resulting from rapid pseudocapacitive intercalation throughout the electrode bulk due to electron delocalization and easy ion transport. Electron delocalization and easy ion transport are facilitated by the high density of redox-active groups in condensed aromatic materials and the alternating arrangement of electron donor and electron acceptor aromatic rings.

[0051] According to one embodiment, a composition is described. The composition comprises an organic material in several embodiments. In one embodiment, for example, the composition comprises a condensed aromatic system. The term “condensed aromatic system” as used herein is given its common meaning in the art and generally refers to two or more cyclic (e.g., monocyclic, bicyclic, tricyclic, etc.) aromatic rings sharing bonds, and / or multiple two or more cyclic (e.g., monocyclic, bicyclic, tricyclic, etc.) aromatic rings sharing bonds. In some embodiments, for example, the condensed aromatic system may comprise one or more condensed aromatic molecules, each containing at least two aromatic rings sharing bonds. As is generally understood by those skilled in the art, the condensed aromatic system may be an extended conjugated system that favorably promotes the delocalization of electronic charge and the diffusion of ionic charge.

[0052] The condensed aromatic system may contain carbon and hydrogen atoms, as is generally understood by those skilled in the art. In some embodiments, the condensed aromatic system may contain one or more heteroatoms that replace the carbon atoms. Suitable examples of heteroatoms include, for example, nitrogen (N), oxygen (O), sulfur (S), and / or selenium (Se).

[0053] According to one embodiment, the condensed aromatic system may have any of a variety of suitable ratios of carbon atoms to heteroatoms (e.g., N, O, S, and / or Se). A relatively low ratio of carbon atoms to heteroatoms (e.g., less than 2) favorably results in more redox active sites in the system compared to a system having a high ratio of carbon atoms to heteroatoms (e.g., greater than 2) but otherwise equivalent, thereby providing sufficient transport pathways for electrical and / or ionic charges through the bulk of the material. In one embodiment, for example, the condensed aromatic system may contain a relatively large number of redox active sites, including, but not limited to, carbonyl groups, amine groups, and / or imine groups. The presence of heteroatoms in the condensed aromatic system may further favorably result in an alternating arrangement of electron donor and electron acceptor aromatic rings, thus facilitating the transport of electrical and / or ionic charges through the bulk of the material.

[0054] In some embodiments, the ratio of carbon atoms to heteroatoms in a condensed aromatic system is greater than 1, greater than or equal to 1.1, greater than or equal to 1.2, greater than or equal to 1.3, greater than or equal to 1.4, greater than or equal to 1.5, greater than or equal to 1.6, greater than or equal to 1.7, greater than or equal to 1.8, or greater than or equal to 1.9. In some embodiments, the ratio of carbon atoms to heteroatoms in a condensed aromatic system is less than 2, less than or equal to 1.9, less than or equal to 1.8, less than or equal to 1.7, less than or equal to 1.6, less than or equal to 1.5, less than or equal to 1.4, less than or equal to 1.2, or less than or equal to 1.1. Combinations of the above-listed ranges are also possible (for example, the ratio of carbon atoms to heteroatoms in a condensed aromatic system is greater than 1 and less than 2, and the ratio of carbon atoms to heteroatoms in a condensed aromatic system is greater than 1.2 and less than 1.4). Other ranges are also possible.

[0055] In some embodiments, at least a portion of the condensed aromatic systems may be linked to one or more hydrogen bonding interactions. In some embodiments, for example, at least a portion of BTABQ molecules, their oligomers, and / or polymers may interact in planar and / or two-dimensional structures via hydrogen bonding. According to some embodiments, the hydrogen bonding interactions may be between one or more hydrogen atoms and one or more oxygen atoms (e.g., of carbonyl groups) and / or one or more nitrogen atoms (e.g., of amine and / or imine groups). Although not bound by theory, the interconnection of condensed aromatic systems via hydrogen bonding interactions may advantageously facilitate electron charge delocalization and ionic charge diffusion through the condensed aromatic systems. In some embodiments, the interconnection of condensed aromatic systems via hydrogen bonding may also advantageously result in solid materials insoluble in organic and aqueous media, thereby providing materials suitable for use in electrodes.

[0056] The condensed aromatic system may have any of a variety of suitable hydrogen bonding interactions. In some embodiments, for example, the number of hydrogen bonding interactions in the condensed aromatic system is greater than or equal to 0.1, greater than or equal to 0.2, greater than or equal to 0.3, greater than or equal to 0.4, greater than or equal to 0.5, greater than or equal to 0.6, greater than or equal to 0.7, greater than or equal to 0.8, or greater than or equal to 0.9 hydrogen bonds per mole of carbon atoms in the condensed aromatic system. In some embodiments, the number of hydrogen bonding interactions in the condensed aromatic system is less than or equal to 1, less than or equal to 0.9, less than or equal to 0.8, less than or equal to 0.7, less than or equal to 0.6, less than or equal to 0.5, less than or equal to 0.4, less than or equal to 0.3, or less than or equal to 0.2 hydrogen bonds per mole of carbon atoms in the condensed aromatic system, and greater than or equal to 0.33 hydrogen bonds, and less than or equal to 1 hydrogen bond per mole of carbon atoms. Combinations of the ranges listed above are also possible (for example, the number of hydrogen bonding interactions in the condensed aromatic system is greater than or equal to 0.1 and less than or equal to 1 hydrogen bonds per mole of carbon atoms in the condensed aromatic system, and the number of hydrogen bonding interactions in the condensed aromatic system is greater than or equal to 0.3 and less than or equal to 0.3 hydrogen bonds per mole of carbon atoms in the condensed aromatic system). Other ranges are also possible. In one embodiment, the number of hydrogen bonding interactions in the condensed aromatic system may be determined by structural and elemental analysis.

[0057] The condensed aromatic system may have any of the various suitable π-π interactions (e.g., donor-acceptor π-π interactions). For example, in one embodiment, at least a portion of the condensed aromatic system is composed of stacked and / or three-dimensional structures via one or more π-π interactions. Although not bound by theory, the interconnection of condensed aromatic systems via π-π interactions may advantageously facilitate electronic charge delocalization and ionic charge diffusion through the condensed aromatic system. In some embodiments, the interconnection of condensed aromatic systems via π-π may also advantageously result in solid materials insoluble in organic and aqueous media, thereby providing materials suitable for use in electrodes.

[0058] In some embodiments, the average interlaminar distance between parts of a condensed aromatic system configured in a stacked and / or three-dimensional structure via one or more π-π interactions may be greater than or equal to 2 Å, greater than or equal to 2.5 Å, greater than or equal to 3 Å, or greater than or equal to 3.5 Å. In some embodiments, the average interlaminar distance between parts of a condensed aromatic system configured in a stacked and / or three-dimensional structure via one or more π-π interactions may be less than or equal to 4 Å, less than or equal to 3.5 Å, less than or equal to 3 Å, or less than or equal to 2.5 Å. Combinations of the above-listed ranges are also possible (for example, the average interlaminar distance between parts of a condensed aromatic system configured in a stacked and / or three-dimensional structure via one or more π-π interactions is greater than or equal to 2 Å and less than or equal to 4 Å, and the average interlaminar distance between parts of a condensed aromatic system configured in a stacked and / or three-dimensional structure via one or more π-π interactions is greater than or equal to 3 Å and less than or equal to 3.5 Å). Other ranges are also possible. In one embodiment, the average interlayer distance between parts of a condensed aromatic system, which is constructed in a stacked and / or three-dimensional structure via one or more π-π interactions, may be determined by structural analysis and / or microscopic methods.

[0059] As described herein, compositions may have low solubility in organic and aqueous solvents at ambient temperature and atmospheric pressure due to hydrogen bonding interactions and / or π-π interactions of the condensed aromatic system, at least partially. In some embodiments, low solubility in organic and aqueous solvents may be advantageous because the condensed aromatic system may be used as an electrode active material.

[0060] The condensed aromatic system may have any of a variety of suitable solubility. In one embodiment, for example, the condensed aromatic system has a solubility of less than or equal to 2 mmol per liter of solvent (e.g., water and / or organic solvent), less than or equal to 1.5 mmol per liter of solvent, less than or equal to 1 mmol per liter of solvent, less than or equal to 0.5 mmol per liter of solvent, or less than or equal to 0.5 mmol per liter of solvent. According to some embodiments, the condensed aromatic system has a solubility of greater than 0 mmol per liter of solvent (e.g., water and / or organic solvent), greater than or equal to 0.1 mmol per liter of solvent, greater than or equal to 0.5 mmol per liter of solvent, greater than or equal to 1 mmol per liter of solvent, or greater than or equal to 1.5 mmol per liter of solvent. Combinations of the ranges listed above are also possible (for example, a condensed aromatic system having a solubility of less than or equal to 2 mmol per liter of solvent and greater than 0 mmol per liter of solvent, and a condensed aromatic system having a solubility of greater than or equal to 0.5 mmol per liter of solvent and less than or equal to 1.5 mmol per liter of solvent). Other ranges are also possible.

[0061] According to some embodiments, the composition has the following structure: [ka] The formula includes molecules (and / or multiple molecules of the above structure), where X is O, S, Se, or NR 1 Selected from the group consisting of R 1 These are each identical or different and selected from the group consisting of hydrogen (-H), optionally substituted alkyl (e.g., -CH3), optionally substituted alkenyl (e.g., -CH=CH2), or optionally substituted alkynyl (e.g., -C≡CH). Tautomers and / or isomers of the structures shown above are also possible in some embodiments.

[0062] In one embodiment, for example, the composition comprises tetraamino-dihydrophenazine-1,4,6,9-tetraone, which is referred to herein as bis-tetraamino-benzoquinone (BTABQ). In one embodiment, BTABQ has the following structure: [ka] It holds.

[0063] In some embodiments, the composition comprises multiple BTABQ molecules. Tautomers and / or isomers of the BTABQ structure shown above are also possible in some embodiments.

[0064] According to one embodiment, BTABQ has the following structure: [ka] It may also be synthesized from the tetraamino-p-benzoquinone (TABQ) molecule.

[0065] TABQ may be commercially purchased and / or synthesized using techniques known to those skilled in the art. According to some embodiments, BTABQ may be formed from TABQ by one-step Michael addition and elimination with ammonia loss.

[0066] According to one embodiment, the composition comprises an oligomer and / or polymer of BTABQ (and / or multiple oligomers and / or polymers of BTABQ). The oligomer and / or polymer of BTABQ may take any of a variety of suitable forms. In some embodiments, for example, the oligomer and / or polymer of BTABQ has the following structure: [ka] In the formula, the dotted lines each independently represent either the bonding of another aromatic ring in the condensed aromatic system or the end of the condensed aromatic system. In some embodiments where the dotted lines represent the bonding of another aromatic ring in the condensed aromatic system, X may be N and R 1 n may be selected from the group consisting of hydrogen (-H), optionally substituted alkyl (e.g., -CH3), optionally substituted alkenyl (e.g., -CH=CH2), or optionally substituted alkynyl (e.g., -C≡CH), and n may be 1. In one embodiment, where the dotted line represents the end of the condensed aromatic system, X is O, S, Se, or NR 1 The group may be selected from the group consisting of R 1 n may be selected from the group consisting of hydrogen (-H), optionally substituted alkyl (e.g., -CH3), optionally substituted alkenyl (e.g., -CH=CH2), or optionally substituted alkynyl (e.g., -C≡CH), and n may be 2. Tautomers and / or isomers of the structure shown above are also possible in some embodiments.

[0067] As is generally understood by those skilled in the art, in one embodiment, where the dotted line represents the bonding of another aromatic ring in the condensed aromatic system, the condensed aromatic system may continue to extend through one or more condensed aromatic rings beyond the aromatic ring formed by the bonding represented by the dotted line.

[0068] In some embodiments, the BTABQ oligomer and / or polymer has the following structure: [ka] is such that when k is greater than 0, X k and Y k is N; when k is 0, X k is O and Y k is NR 1 ; when l is greater than 0, X l and Y l is N; when k is 0, X l is O and Y l is NR 1 ; when m is greater than 0, X m and Y<00000...​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​The structure of the BTABQ oligomer and / or polymer may, in some embodiments, be determined based on elemental analysis, matrix-assisted laser desorption / ionization-time-of-flight (MALDI-TOF) mass spectrometry, and / or X-ray photoelectron spectroscopy.

[0072] According to one embodiment, oligomers and / or polymers of BTABQ may be synthesized by polycondensation of BTABQ in the presence of heat and reduced water. In some embodiments, the polycondensation reaction may be a ladder reaction.

[0073] According to several embodiments, electrodes are described. In some embodiments, the electrodes are or comprise an electrochemically active charge storage material. As will be described in further detail herein, the electrodes may, in some embodiments, be arranged in an electrochemical cell (e.g., a battery) and / or a charge storage device (e.g., a capacitor).

[0074] Figure 1 shows a schematic diagram of an electrode according to one embodiment. In one embodiment, electrode 102 is a composite electrode comprising at least two different (e.g., chemically distinct) materials. In some embodiments, electrode 102 comprises, for example, an active material 104. In some embodiments, the active material is or comprises a composition described herein. In some embodiments, the active material comprises, for example, an organic material (e.g., BTABQ, and / or condensed aromatic systems such as tautomers, oligomers, and / or polymers thereof). According to some embodiments, electrode 102 may contain one or more additives.

[0075] A composite electrode (e.g., an electrochemically active charge storage material) may contain an active material in any of a variety of suitable amounts. In some embodiments, for example, the composite electrode contains the active material in an amount greater than or equal to 50 weight percent (wt%), greater than or equal to 60 wt%, greater than or equal to 70 wt%, greater than or equal to 80 wt%, greater than or equal to 90 wt%, or greater than or equal to 95 wt%, relative to the total weight of the composite electrode. In some embodiments, the composite electrode contains the active material in an amount less than or equal to 99 wt%, less than or equal to 95 wt%, less than or equal to 90 wt%, less than or equal to 80 wt%, less than or equal to 70 wt%, or less than or equal to 60 wt%, relative to the total weight of the composite electrode. Combinations of the ranges listed above are also possible (for example, a composite electrode containing active material in an amount greater than or equal to 50% by weight and less than or equal to 99% by weight relative to the total weight of the composite electrode, or a composite electrode containing active material in an amount greater than or equal to 80% by weight and less than or equal to 90% by weight relative to the total weight of the composite electrode). Other ranges are also possible.

[0076] As described above, a composite electrode (e.g., an electrochemically active charge storage material) may contain one or more additives. Suitable additives include, but are not limited to, conductive species and / or binders. Suitable conductive species include, for example, conductive carbon materials (e.g., acetylene black carbon). In some embodiments, a suitable binder includes a polymer (e.g., polyvinylidene fluoride).

[0077] A composite electrode (e.g., an electrochemically active charge storage material) contains one or more additives in any of a variety of suitable amounts. In some embodiments, for example, the composite electrode contains one or more additives in amounts greater than or equal to 1% by weight, greater than or equal to 10% by weight, greater than or equal to 20% by weight, greater than or equal to 30% by weight, or greater than or equal to 40% by weight, relative to the total weight of the composite electrode. In some embodiments, the composite electrode contains one or more additives in amounts less than or equal to 50% by weight, less than or equal to 40% by weight, less than or equal to 30% by weight, less than or equal to 20% by weight, or less than or equal to 10% by weight, relative to the total weight of the composite electrode. Combinations of the ranges listed above are possible (for example, a composite electrode containing one or more additives in an amount greater than or equal to 1% by weight and less than or equal to 50% by weight relative to the total weight of the composite electrode, or a composite electrode containing one or more additives in an amount greater than or equal to 10% by weight and less than or equal to 30% by weight relative to the total weight of the composite electrode). Other ranges are also possible.

[0078] The electrodes described herein may be prepared using techniques known to those skilled in the art. In one embodiment, for example, electrode materials in appropriate ratios may be mixed, coated onto a substrate, and dried. In one non-limiting embodiment, for example, an active material, a conductive material, and a binder may be mixed in an organic solvent in a ratio of 8:1:1, coated onto a carbon substrate, and dried.

[0079] According to one embodiment, an electrochemical cell is described. As is generally understood by those skilled in the art, the electrochemical cell may include one or more electrodes (e.g., one or more electrochemically active charge-storing materials). In one embodiment, the electrochemical cell is a battery (e.g., a rechargeable or non-rechargeable battery).

[0080] Figure 2 shows a schematic diagram of an electrochemical cell according to one embodiment. In some embodiments, the electrochemical cell 202 includes a first electrode 102a and a second electrode 102b. The first electrode 102a and the second electrode 102b may be housed in a housing 208 in some embodiments. In some embodiments, at least one of the first electrode 102a and / or the second electrode 102b contains an active material comprising a composition described herein. In some embodiments, for example, the active material of at least one electrode includes an organic material (e.g., BTABQ, and / or condensed aromatic systems such as its tautomers, oligomers, and / or polymers).

[0081] According to some embodiments, the electrochemical cell 202 includes an electrolyte 204. In some embodiments, the electrolyte 204 may be located within a housing 208. In some embodiments, the electrolyte 204 is a liquid electrolyte. In other embodiments, the electrolyte 204 is a solid electrolyte. Further details regarding liquid and solid electrolytes are described herein.

[0082] The liquid electrolyte may have any of a variety of suitable pH values. In some embodiments, for example, the liquid electrolyte is sufficiently acidic and has a pH greater than or equal to 0, greater than or equal to 0.5, greater than or equal to 1, or greater than or equal to 1.5. In some embodiments, the liquid electrolyte is sufficiently acidic and has a pH less than or equal to 2, less than or equal to 1.5, less than or equal to 1, or less than or equal to 0.5. Combinations of the above-listed ranges are possible (for example, the liquid electrolyte is sufficiently acidic and has a pH greater than or equal to 0 and less than or equal to 2, and the liquid electrolyte is sufficiently acidic and has a pH greater than or equal to 1 and less than or equal to 1.5). Other ranges are also possible.

[0083] According to some embodiments, the liquid electrolyte may be sufficiently basic and have a pH greater than or equal to 12, greater than or equal to 12.5, greater than or equal to 13, greater than or equal to 13.5, greater than or equal to 14, or greater than or equal to 14.5. In some embodiments, the liquid electrolyte is sufficiently basic and has a pH less than or equal to 15, less than or equal to 14.5, less than or equal to 14, less than or equal to 13.5, less than or equal to 13, or less than or equal to 12.5. Combinations of the above-listed ranges are possible (for example, the liquid electrolyte is sufficiently basic and has a pH greater than or equal to 12 and less than or equal to 15, and the liquid electrolyte is sufficiently basic and has a pH greater than or equal to 13 and less than or equal to 13.5). Other ranges are also possible.

[0084] In some embodiments, the pH of the liquid electrolyte may be determined using a pH meter.

[0085] As will be explained in more detail below, liquid electrolytes with a sufficiently acidic pH (e.g., greater than or equal to 0 and less than 2) and / or a sufficiently basic pH (e.g., greater than 12 and less than or equal to 14) may favorably improve the charge capacity of electrodes placed in the liquid electrolyte compared to neutral pH values ​​(e.g., greater than or equal to 4 and less than or equal to 10).

[0086] In some embodiments, the electrochemical cell 202 includes a separator 206 positioned between a first electrode 102a and a second electrode 102b. In some embodiments, the separator 206 may be located within a housing 208. Further details regarding the separator are described herein.

[0087] According to one embodiment, a charge storage device is described. As is generally understood by those skilled in the art, the charge storage device comprises, in some embodiments, one or more electrodes (e.g., one or more electrochemically active charge storage materials). The charge storage device may, in some embodiments, be a capacitor or a supercapacitor.

[0088] Figure 3 shows a schematic diagram of a charge storage device according to one embodiment. In some embodiments, the charge storage device 302 includes a first electrode 102a and a second electrode 102b. In some embodiments, at least one of the first electrode 102a and / or the second electrode 102b includes an active material comprising a composition described herein. In some embodiments, for example, the active material includes an organic material (e.g., BTABQ, and / or condensed aromatic systems such as its tautomers, oligomers, and / or polymers).

[0089] In some embodiments, the charge storage device 302 includes an insulator 304 positioned between a first electrode 102a and a second electrode 102b. According to one embodiment, the insulator 304 may be a dielectric material.

[0090] The electrode (e.g., an electrochemically active charge storage material) may have any of a variety of suitable conductivity. In some embodiments, for example, the electrode is 10 -8 Greater than or equal to S / cm, 10 -7 Greater than or equal to S / cm, 10 -6 Greater than or equal to S / cm, 10 -5 Greater than or equal to S / cm, 10 -4 Greater than or equal to S / cm, or 10 -3 It has a conductivity greater than or equal to S / cm. In one embodiment, the electrode is 10 -2 Less than or equal to S / cm, 10 -3 Less than or equal to S / cm, 10 -4Less than or equal to S / cm, 10 -5 Less than or equal to S / cm, 10 -6 Less than or equal to S / cm, or 10 -7 It has a conductivity less than or equal to S / cm. Combinations of the ranges listed above are possible (for example, the electrodes are 10 -8 Greater than or equal to S / cm, 10 -2 The electrodes have conductivity less than or equal to S / cm, and the electrodes are 10 -6 Greater than or equal to S / cm, 10 -4 (Having a conductivity less than or equal to S / cm). Other ranges are also possible. The conductivity of the electrode may be determined using a conductivity meter in some embodiments.

[0091] The electrode (e.g., an electrochemically active charge-storing material) may have any of a variety of suitable specific capacities. In some embodiments, for example, the electrode has a specific capacity of greater than or equal to 200F, greater than or equal to 250F, greater than or equal to 300F, greater than or equal to 350F, greater than or equal to 400F, greater than or equal to 450F, greater than or equal to 500F, greater than or equal to 550F, greater than or equal to 600F, or greater than or equal to 650F per gram of active material. In some embodiments, the electrode has a specific capacity of less than or equal to 700F, less than or equal to 650F, less than or equal to 600F, less than or equal to 550F, less than or equal to 500F, less than or equal to 450F, less than or equal to 400F, less than or equal to 350F, less than or equal to 300F, or less than or equal to 250F per gram of active material. Combinations of the ranges listed above are possible (for example, the electrode has a specific capacitance greater than or equal to 200 F and less than or equal to 700 F per gram of active material, and the electrode has a specific capacitance greater than or equal to 500 F and less than or equal to 550 F per gram of active material). Other ranges are also possible. In some embodiments, the specific capacitance may be calculated from cyclic voltammetry (CV) data by the following formula: C = Q / (Vm), where C(F / g) is the specific capacitance, m(g) is the mass of the active material, Q(C) is the average charge during the charge-discharge process, and V(V) is the potential window. According to some embodiments, the specific capacitance is measured at a scanning speed of 0.2 mV / s.

[0092] The electrode (e.g., an electrochemically active charge-storing material) may have any of a variety of suitable cycle performances. In some embodiments, for example, the electrode may have a cycle performance of greater than or equal to 10,000 cycles, greater than or equal to 20,000 cycles, greater than or equal to 30,000 cycles, greater than or equal to 40,000 cycles, greater than or equal to 50,000 cycles, greater than or equal to 60,000 cycles, greater than or equal to 70,000 cycles, greater than or equal to 80,000 cycles, or greater than or equal to 90,000 cycles. In one embodiment, the electrode has a cycle performance of less than or equal to 100,000 cycles, less than or equal to 90,000 cycles, less than or equal to 80,000 cycles, less than or equal to 70,000 cycles, less than or equal to 60,000 cycles, less than or equal to 50,000 cycles, less than or equal to 40,000 cycles, less than or equal to 30,000 cycles, or less than or equal to 20,000 cycles. Combinations of the above-listed ranges are possible (for example, the electrode has a cycle performance of greater than or equal to 10,000 cycles and less than or equal to 100,000 cycles, and the electrode has a cycle performance of greater than or equal to 30,000 cycles and less than or equal to 40,000 cycles). Other ranges are also possible. According to one embodiment, the cycle performance may be measured at a scanning speed of 30 mV / s.

[0093] As described above, the condensed aromatic system may contain multiple carbon atoms, hydrogen atoms, and one or more heteroatoms (e.g., N, O, S, and / or Se) that replace the carbon atoms. The heteroatoms may function as redox active sites that advantageously facilitate electric and / or ion transport through the bulk of the material. In some embodiments, the molar ratio of electrons accumulated as charge per mole of heteroatoms in the condensed aromatic system is greater than or equal to 0.1, greater than or equal to 0.2, greater than or equal to 0.3, greater than or equal to 0.4, greater than or equal to 0.5, greater than or equal to 0.6, or greater than or equal to 0.7. In some embodiments, the molar ratio of electrons accumulated as charge per mole of heteroatoms in the condensed aromatic system is less than or equal to 0.8, less than or equal to 0.7, less than or equal to 0.6, less than or equal to 0.5, less than or equal to 0.4, less than or equal to 0.3, or less than or equal to 0.2. Combinations of the ranges listed above are also possible (for example, the molar ratio of electrons accumulated as charge per mole of heteroatoms in a condensed aromatic system is greater than or equal to 0.1 and less than or equal to 0.8, and the molar ratio of electrons accumulated as charge per mole of heteroatoms in a condensed aromatic system is greater than or equal to 0.3 and less than or equal to 0.6). Other ranges are also possible.

[0094] The composite electrode (e.g., an electrochemically active charge storage material) may have any of a variety of suitable charge capacities per gram of active material. In one embodiment, for example, the composite electrode has a charge capacity of greater than or equal to 50 mAh, greater than or equal to 100 mAh, greater than or equal to 150 mAh, greater than or equal to 200 mAh, greater than or equal to 250 mAh, greater than or equal to 300 mAh, or greater than or equal to 350 mAh per gram of active material. In some embodiments, the composite electrode has a charge capacity of less than or equal to 400 mAh, less than or equal to 350 mAh, less than or equal to 300 mAh, less than or equal to 250 mAh, less than or equal to 200 mAh, less than or equal to 150 mAh, or less than or equal to 50 mAh. Combinations of the ranges listed above are possible (for example, a composite electrode having a charge capacity greater than or equal to 50 mAh and less than or equal to 400 mAh per gram of active material, and a composite electrode having a charge capacity greater than or equal to 150 mAh and less than or equal to 200 mAh per gram of active material). Other combinations are also possible.

[0095] A composite electrode (e.g., an electrochemically active charge storage material) may have any of a variety of suitable charge capacities per gram of composite electrode. In some embodiments, for example, the composite electrode has a charge capacity of greater than or equal to 30 mAh, greater than or equal to 50 mAh, greater than or equal to 100 mAh, greater than or equal to 150 mAh, greater than or equal to 200 mAh, greater than or equal to 250 mAh, or greater than or equal to 300 mAh per gram of composite electrode. In some embodiments, the composite electrode has a charge capacity of less than or equal to 350 mAh, less than or equal to 300 mAh, less than or equal to 250 mAh, less than or equal to 200 mAh, less than or equal to 150 mAh, less than or equal to 100 mAh, or less than or equal to 50 mAh per gram of composite electrode. Combinations of the ranges listed above are possible (for example, a composite electrode having a charge capacity greater than or equal to 30 mAh and less than or equal to 350 mAh per gram of composite electrode, and a composite electrode having a charge capacity greater than or equal to 100 mAh and less than or equal to 150 mAh per gram of composite electrode). Other combinations are also possible.

[0096] According to one embodiment, the above-mentioned charge capacity (i.e., charge capacity per gram of active material and / or charge capacity per gram of composite electrode) may be discharged at relatively fast charge and / or discharge rates compared to conventional capacitor systems. In some embodiments, for example, the charge capacity is discharged at charge and / or discharge rates of less than 60 seconds, less than 50 seconds, less than 40 seconds, less than 30 seconds, or less than 20 seconds. In one embodiment, the charge capacity is discharged at charge and / or discharge rates longer than or equal to 10 seconds, longer than or equal to 20 seconds, longer than or equal to 30 seconds, longer than or equal to 40 seconds, or longer than or equal to 50 seconds. Combinations of the above-listed ranges are also possible (for example, the charge capacity is discharged at charge and / or discharge rates of less than or equal to 60 seconds and longer than or equal to 10 seconds, and the charge capacity is discharged at charge and / or discharge rates of longer than or equal to 30 seconds and shorter than or equal to 40 seconds). Other ranges are also possible.

[0097] As described above, the electrodes described herein (e.g., electrochemically active charge storage materials) may be placed in an electrochemical cell containing an electrolyte (e.g., a liquid electrolyte). In some embodiments, the liquid electrolyte may have a sufficiently acidic pH (e.g., greater than or equal to 0 and less than 2) or a sufficiently basic pH (e.g., greater than 12 and less than or equal to 14). In some such embodiments, the electrode may have a greater charge capacity than an electrode placed in an electrochemical cell containing a liquid electrolyte having a pH greater than or equal to 2 and less than or equal to 12, but otherwise equivalent. Although not bound by theory, the increased charge capacity at sufficiently acidic and / or sufficiently basic liquid electrolyte pH values ​​may result from the rapid pseudocapacitive intercalation of cations and / or anions across the bulk of the electrode.

[0098] In some embodiments, for example, the electrode has a charge capacity that is at least 20% greater, at least 30% greater, at least 40% greater, at least 50% greater, at least 60% greater, at least 70% greater, at least 80% greater, or at least 90% greater when the pH of the liquid electrolyte is greater than 0, less than 2, greater than 12, or less than 15, compared to when the pH of the liquid electrolyte is greater than 2 and less than 12. In some embodiments, the electrode has a charge capacity that is less than 100% greater, less than 90% greater, less than 80% greater, less than 70% greater, less than 60% greater, less than 50% greater, less than 40% greater, or less than 30% greater when the pH of the liquid electrolyte is greater than 2 and less than 12, compared to when the pH of the liquid electrolyte is greater than 2 and less than 12. Combinations of the ranges listed above are also possible (for example, the electrode has a charge capacity that is at least 20% greater and less than 100% greater when the pH of the liquid electrolyte is greater than or equal to 0, less than or equal to 2, greater than or equal to 12, and less than or equal to 15, compared to when the pH of the liquid electrolyte is greater than 2 and less than 12; and the electrode has a charge capacity that is at least 40% greater and less than or equal to 60% greater when the pH of the liquid electrolyte is greater than or equal to 0, less than or equal to 2, greater than or equal to 12, and less than or equal to 15, compared to when the pH of the liquid electrolyte is greater than 2 and less than 12). Other ranges are also possible.

[0099] In some embodiments, the electrode (e.g., an electrochemically active charge storage material) may favorably retain a high amount of charge capacity after the electrode cycle. In some embodiments, for example, the electrode has a charge capacity retention rate greater than or equal to 75%, greater than or equal to 80%, greater than or equal to 85%, greater than or equal to 90%, or greater than or equal to 95% after at least 20,000 cycles. In some embodiments, the electrode has a charge capacity retention rate less than or equal to 99%, less than or equal to 95%, less than or equal to 90%, less than or equal to 85%, or less than or equal to 80% after at least 20,000 cycles. Combinations of the ranges listed above are also possible (for example, the electrodes have a charge capacity retention rate greater than or equal to 75% and less than 99% after at least 20,000 cycles, and the electrodes have a charge capacity retention rate greater than or equal to 85% and less than or equal to 95% after at least 20,000 cycles). Other ranges are also possible.

[0100] According to one embodiment, the electrode (e.g., an electrochemically active charge storage material) may advantageously release its sufficiently high charge capacity. In some embodiments, for example, the electrode is 2.0V vs. Li + At a voltage higher than that of the Li standard reference electrode, it releases at least 80%, at least 85%, at least 90%, at least 95%, or at least 99% of its charge capacitance. In one embodiment, the electrode is 2.0V vs. Li + At a voltage higher than the Li standard reference electrode, it releases an amount less than 100%, less than or equal to 99%, less than or equal to 95%, less than or equal to 90%, or less than or equal to 85% of its charge capacitance. Combinations of the above listed ranges are also possible (e.g., the electrode is 2.0V vs. Li). +At a voltage higher than the Li standard reference electrode, the electrode discharges at least 80% and less than 100% of its charge capacity, and the electrode is 2.0V vs. Li + (At a voltage higher than that of the Li standard reference electrode, it releases at least 85% and less than 95% of its charge capacity). Other ranges are also possible.

[0101] As noted above, in some embodiments, the electrochemical cell and / or charge storage device described herein may include one or more electrodes. For example, in some embodiments, the electrochemical cell and / or charge storage device includes an anode and a cathode.

[0102] The anode may contain various anodic active materials. As used herein, the term "anodic active material" refers to any electrochemically active species associated with the anode.

[0103] In some embodiments, the anode has a thickness of less than or equal to 1500 micrometers, less than or equal to 1250 micrometers, less than or equal to 1000 micrometers, less than or equal to 750 micrometers, less than or equal to 500 micrometers, or less than or equal to 200 micrometers. In some embodiments, the anode has a thickness of at least 1 micrometer, at least 5 micrometers, at least 10 micrometers, at least 25 micrometers, at least 50 micrometers, at least 100 micrometers, or at least 150 micrometers. Combinations of the above ranges are also possible (e.g., 1 micrometer to 1500 micrometers). Other ranges are also possible.

[0104] The cathode may contain various cathode active materials. As used herein, the term “cathode active material” refers to any electrochemically active species associated with the cathode.

[0105] In some embodiments, the cathode may have a thickness of less than or equal to 2000 micrometers, less than or equal to 1500 micrometers, less than or equal to 1250 micrometers, less than or equal to 1000 micrometers, less than or equal to 750 micrometers, less than or equal to 500 micrometers, or less than or equal to 200 micrometers. In some embodiments, the cathode may have a thickness of at least 1 micrometer, at least 5 micrometers, at least 10 micrometers, at least 25 micrometers, at least 50 micrometers, at least 100 micrometers, or at least 150 micrometers. Combinations of the above ranges are also possible (e.g., 1 micrometer to 2000 micrometers). Other ranges are also possible.

[0106] As described herein, electrochemical cells may, in some embodiments, include an electrolyte. As is generally understood by those skilled in the art, the electrolyte used in an electrochemical cell can function as a medium for ion storage and transport, and in the special case of solid and / or gel electrolytes, these materials may further function as a separator between the anode and the cathode. Any liquid, solid, or gel material capable of storing and transporting ions may be used insofar as it facilitates ion transport between the anode and the cathode. Electrolytes are generally electron-nonconductive to prevent short circuits between the anode and the cathode. The electrolyte may include one or more liquid electrolyte solvents, gel polymer materials, or polymer materials. The electrolyte may also include one or more ionic electrolyte salts, which may result in and / or enhance ionic conductivity.

[0107] In some cases, the electrochemical cell contains a liquid electrolyte.

[0108] In one embodiment, the liquid electrolyte is an aqueous electrolyte (e.g., water). In some embodiments, the aqueous electrolyte may contain other components, such as one or more ionic electrolyte salts (e.g., to provide and / or enhance ionic conductivity).

[0109] In some embodiments, the electrolyte comprises a non-aqueous electrolyte. A suitable non-aqueous electrolyte comprises an organic liquid electrolyte solvent. These electrolytes may optionally contain one or more ionic electrolyte salts (e.g., to provide and / or enhance ionic conductivity). Examples of useful non-aqueous organic liquid electrolyte solvents include, but are not limited to, acetonitrile. This disclosure is not intended to limit us in this respect, and other non-aqueous organic liquid electrolyte solvents are possible.

[0110] According to one embodiment, the electrochemical cell comprises a solid and / or gel electrolyte. For example, in some embodiments, one or more solid polymers can be used to form the solid and / or gel electrolyte.

[0111] The electrolyte may further contain one or more ionic electrolyte salts commonly known in the art to provide and / or improve the ionic conductivity of the electrolyte. For example, in some cases the ionic electrolyte salts may be chloride salts (e.g., NaCl), hydrogen phosphate salts (Na2HPO4), carbonate salts (Na2CO3), and / or citric acid. This disclosure is not intended to limit it in this respect, and other ionic electrolyte salts are also possible.

[0112] In some embodiments, the electrochemical cell includes a separator. The separator generally comprises a polymer material. In some embodiments, the separator is located between the electrolyte and the electrodes (e.g., a first electrode, a second electrode, an anode, a cathode). The separator can be configured to suppress (e.g., prevent) physical contact between the first electrode and the second electrode that could cause a short circuit in the electrochemical cell. The separator can be configured to be substantially electron-nonconductive, which can suppress the extent to which the separator causes a short circuit in the electrochemical cell.

[0113] The following examples are intended to illustrate certain embodiments of the present invention, but are not intended to illustrate the entire scope of the invention. [Examples]

[0114] (Example 1) The following examples describe the synthesis and properties of bis-tetraamino-benzoquinone (BTABQ) molecules and their polymer (pBTABQ).

[0115] Condensed aromatic materials, including BTABQ and pBTABQ, may be used as electrodes for electrochemical energy storage (EES). The materials have a high density of redox-active quinone / imine groups (e.g., C:(N / O)<1.3) in an aromatic molecular backbone with extended conjugation (Figure 4), forming insoluble solids in both organic and aqueous media through strong intermolecular hydrogen bonding and donor-acceptor (DA)π-π interactions (Figure 5). BTABQ and pBTABQ exhibit excellent charge storage capacity at high charge-discharge rates in a variety of electrolytes, and due to excellent electron delocalization and easy ion transport, even practical mass loading arises primarily from rapid pseudocapacitive intercalation across the electrode bulk (Figure 6).

[0116] One-step Michael addition and elimination of tetraaminobenzoquinone (TABQ) yields BTABQ on a gram scale (Figure 4). BTABQ is highly insoluble in common organic solvents, yet appears as crystalline microrods, as revealed by powder X-ray diffraction (PXRD) (Figure 7). The crystalline structure of BTABQ was obtained by Pawley refinement and continuous rotational electron diffraction (cRED) of synchrotron PXRD data using the ab initio method. The high resolution of the cRED dataset allows for the direct positioning of all non-hydrogen atoms down to 0.625 Å. BTABQ possesses a planar condensed aromatic skeleton, where each BTABQ molecule is closely surrounded by six neighbors, forming a two-dimensional (2D) layer via strong intermolecular hydrogen bonds (Figure 8). The 2D layers stack via donor-acceptor (DA) π-π interactions with a slight interlayer separation of 3.14 Å (Figures 9 and 10). Experimental indicators of BTABQ single crystals show that the long axis of the crystal aligns with the (102) crystallographic direction (i.e., perpendicular to the 2D layer), while its cross-section is parallel to the 2D layer. Exfoliated BTABQ crystals further demonstrate the 2D layered nature. In conclusion, the anisotropic crystal growth and 2D nature of BTABQ indicate that intermolecular hydrogen bonding is stronger than interlayer π-π stacking. Overall, the high-density, energetically favorable solid packing of BTABQ provides potential for efficient electron delocalization.

[0117] Given the proximity of amino and carbonyl groups in the 2D layer, it was hypothesized that BTABQ could undergo solid polycondensation to produce more expandable material. The thermogravimetric profile of BTABQ revealed significant weight loss at approximately 300°C, supporting the possibility of such ring condensation. Indeed, heating BTABQ at approximately 300°C under vacuum for two days resulted in the complete consumption of BTABQ and the formation of an amorphous solid (pBTABQ) while maintaining unchanged particle size and morphology. pBTABQ has a significantly higher molecular weight and lower oxygen content than BTABQ, as predicted by water loss during laddering. Pair distribution function analysis of both materials revealed their similar local structures, showing that pBTABQ has a high-concentration solid-state arrangement of molecular fragments similar to BTABQ, despite the lack of long-range order. High-magnification Cryo-EM images of pBTABQ confirmed its disordered but high-concentration solid packing. Surprisingly, pBTABQ exhibits even stronger hydrogen bonding interactions similar to BTABQ. Gas sorption research has shown that both materials have a low specific surface area of ​​approximately 20 m². 2 Assuming a density of / g, we demonstrate that it is non-porous. Ultimately, the various properties confirm that pBTABQ is a disordered oligomeric analog of BTBAQ, possessing an extended aromatic skeleton, rich carbonyl / imine redox sites, strong hydrogen bonding, and high-concentration solid packing.

[0118] The electronic properties of BTABQ and pBTABQ are characterized by diffuse reflectance UV-Vis (DRUV-Vis) spectroscopy. Both materials exhibit broad absorption around approximately 520 and 800 nm (Figure 11). The former arises from intraquinone transitions, while the latter is accounted for by extended conjugation within the condensed aromatic framework of BTABQ and pBTABQ. Surprisingly, both materials show significant absorption in the near-infrared region (NIR), resulting in narrow optical band gaps of 0.82 eV and 0.79 eV for BTABQ and pBTABQ, respectively (Figure 11, inset). The very strong NIR adsorption is mainly due to extended conjugation, strong intermolecular hydrogen bonding, and bulk electron delocalization via π-π stacking. In particular, pBTABQ also shows considerable absorption in the mid-infrared region (MIR) due to its extended aromatic core and large dispersion of the corresponding electron bands, demonstrating excellent electron delocalization.

[0119] BTABQ and pBTABQ are 2.4 × 10⁻⁶ at room temperature. -5 Scm -1 and 0.79 × 10 -6 Scm -1 The intrinsic bulk conductivity of each material is shown. Electron paramagnetic resonance (EPR) spectra show very strong isotropic signals for organic radicals in both materials, with pBTABQ showing significantly higher signal intensity than BTABQ. Along with very strong Drude-type background MIR absorption, pBTABQ has a higher free carrier concentration, as revealed by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Overall, the efficient incorporation of high-density redox sites into extended conjugated structures through electron delocalization makes BTABQ and pBTABQ promising candidates for high-rate EES.

[0120] (Example 2) The following examples describe the electrochemistry of systems using materials containing BTABQ molecules and pBTABQ in a neutral electrolyte.

[0121] Cyclic voltammograms (CVs) of BTABQ and pBTABQ were obtained using a three-electrode structure with a 1M LiCl aqueous electrolyte, with values ​​ranging from 0.2 to 30 mVs. -1 The curve is nearly rectangular at scanning speeds within this range (Figure 12). BTABQ and pBTABQ show stable currents at reduction potential windows of 0.5V and 1.0V, respectively. The law of exponents is given by (i=av). b Analysis of the CV current (i) at different scanning speeds (v) using ) reveals a near-single b value for both materials, indicating that the charge accumulation action is not limited by ion diffusion. Overall, the electrochemical behavior of BTABQ and pBTABQ is inherently different from the sharp redox features and diffusion-limited behavior generally observed for organic molecules with carbonyl or imine groups. Instead, these features are similar to the behavior reported for inorganic materials such as RuO2·nH2O and MXenes, which exhibit a capacitive but rapid redox charge accumulation mechanism and pseudocapacitance. Indeed, both BTABQ and pBTABQ exhibit a low specific surface area (<20 m²). 2 g -1 ) has 0.2mVs -1 Approximately 510 Fg -1 and 10mVs -1 Approximately 300 Fg -1 It shows a high weight-specific capacity calculated from the CV (Figure 13 (insert diagram)), suggesting the possibility of a pseudocapacitive charge storage mechanism. 2~10Ag -1 Constant current charge-discharge (GCD) experiments at current densities in the range of 30mVs show triangular wave voltage-time profiles, confirming their high capacitance. Furthermore, both materials exhibit high capacitance at 30mVs. -1 CV at high scanning speed (Figure 13) and 10Ag -1 This demonstrates excellent capacitance retention over 20,000 cycles in GCD experiments at the given current density.

[0122] The observed charge accumulation behavior was further evaluated under dynamic conditions using electrochemical impedance spectra (EIS) at various negative potentials. Nyquist plots of impedance for both BTABQ and pBTABQ (Figure 14) show typical capacitive features with low equivalent series resistance (approximately 1–2 Ω), a short semicircle, and a 45° transition region, along with an extended 90° capacitive region at low frequencies. On the other hand, the semicircle in the high-frequency region reveals a diameter that decreases when a negative potential is applied, confirming that rapid charge transfer events occur during charge accumulation in both materials. Overall, the EIS and CV of BTABQ and pBTABQ exhibit capacitive features, highlighting the possibility of a pseudocapacitive charge accumulation mechanism.

[0123] The redox process during charge accumulation was analyzed by excituated X-ray photoelectron spectroscopy (XPS) and solid-state nuclear magnetic resonance (ssNMR) studies of the initial and negatively polarized electrodes. The amino functional groups in initial BTABQ and pBTABQ exhibit partial imine characteristics due to ketoenol tautomerization, as confirmed by an imine carbon-chemical shift at 146.4 ppm in the ssNMR of BTABQ and the N1s XPS spectra of both materials. Analysis of the O1s XPS spectra of the polarized electrodes revealed a significant decrease in the intensity of the C=O peak and CO -The appearance of peaks reveals the reduction of the carbonyl group. Analysis of the N1s spectrum shows the disappearance of the imine component and the growth of the benzoid-amine component upon reduction. ssNMR of polarized BTABQ further confirms that both the carbonyl and imine groups are redox active sites for charge accumulation in BTABQ and pBTABQ. The charges accumulated at these redox active sites are delocalized both intramolecularly within the condensed aromatic skeleton and intermolecularly via hydrogen bonding and D-Aπ-π stacking, appearing clearly in a nearly rectangular CV. In contrast, small organic molecules with localized electronic structures exhibit well-defined, sharp redox features. Furthermore, larger π-conjugated organic molecules with close π-π stacking, such as 5,7,12,14-pentanetetron, lack hydrogen bonding interactions, limiting electron delocalization and resulting in sharp, well-separated redox peaks in their CV.

[0124] The pseudocapacitance properties in BTABQ and pBTABQ were investigated by spectroscopic studies as surface-bound or intercalation-system bulk action. The in situ wide-angle X-ray scattering (WAXS) pattern of negatively polarized BTABQ shows a significant shift of (10²) reflection to lower 2θ values ​​(Figure 15). + The increase in the spacing between the 2D layers of BTABQ during insertion supports the intercalation system charge accumulation mechanism. Notably, as confirmed by excitatory energy dispersive X-ray spectroscopy (EDS) studies of the polarized sample, Na + and Mg 2+ Other cations, such as those mentioned above, can also be inserted into both materials (Figure 16). Elemental mapping shows that a substantial amount of metal cations are uniformly distributed throughout the particles, highlighting the bulk charge accumulation in both BTABQ and pBTABQ electrodes.

[0125] A comprehensive understanding of the roles of electrolyte ions and solvents in intercalation has been sought through electrochemical studies in various electrolytes. Both materials exhibit largely similar CVs in different alkaline or alkaline earth electrolytes. However, significantly lower currents in CV are observed in tetraethylammonium (TEA). + ) Obtained using an electrolyte containing cations. TEA + Li + Replacing the increased amount resulted in an increase in CV current. Overall, these results suggest that both materials can insert a variety of alkali and alkaline earth ions, but a larger TEA + This demonstrates the ability to exclude ions (Figure 18). The ability of these BTABQ and pBTABQ to insert multiple cations and exhibit size-based sieve behavior is similar to the reported behavior of MXenes and coordination polymers that exhibit intercalation pseudocapacity.

[0126] The role of the solvent in intercalation was investigated by CV with organic and aqueous electrolytes. The CV of pBTABQ recorded in a 1 M sodium perchlorate (NaClO4) solution of acetonitrile (MeCN) showed substantially lower currents than those recorded under aqueous conditions (Figure 17). Adding 1% or 5% water to MeCN resulted in a significant increase in the observed current. However, water does not lead to TEA + No similar improvement was observed when added to electrolytes containing [the substance]. These results suggest a crucial role for water in cation intercalation into BTABQ and pBTABQ. Specifically, water can function as a cointercalant that facilitates the intercalation and diffusion of metal cations without causing significant structural distortion of the electrode material, similar to the water-assisted intercalation of metal cations into vanadium oxide and Prussian blue analogues (PBA). The cointercalation of water molecules, possibly as part of the hydration sphere of the inserted cation (Figure 18), is facilitated by the hydrogen bonding network in BTABQ and pBTABQ, which may further improve the total amount of accumulated charge.

[0127] (Example 3) The following examples describe the effect of pH on charge accumulation in systems using materials containing BTABQ molecules and pBTABQ.

[0128] Electrolyte pH has been shown to strongly influence the charge accumulation behavior of pseudocapacitive materials. Considering the strong roles of hydrogen bonding and water cointercalation in BTABQ and pBTABQ, the effect of pH on their electrochemical behavior was evaluated using aqueous NaCl electrolytes with a broad pH range of 0–14.7. While both materials exhibit similar pH-dependent behavior, the following discussion focuses primarily on pBTABQ, considering its larger electrochemical window (1V).

[0129] The CV recorded in electrolytes with intermediate pH remains nearly rectangular, while the CV recorded under strongly acidic and alkaline conditions exhibits broad redox features with poor peak separation and significantly increased current density (Figure 19). Specifically, two sets of broad redox peaks are shown at pH 0 and 1, while a single broad redox feature is observed at pH 13 and 14.7. From the aforementioned peak current versus scanning rate analysis, we found b values ​​of approximately 0.9 at low and high pH (Figure 20), indicating that charge accumulation is not yet limited by bulk ion diffusion. Accumulation occurs at different pH levels, with values ​​of 0.2 mVs. -1 From CV to weight-to-weight capacity (mAhg) -1 The total amount of charge calculated as ) is approximately 160 mAhg at the intermediate pH. -1 From pH 14.7 and 0, 272 and 310 mAhg -1 The values ​​increase, each showing a U-shaped curve (Figure 21). Such pH dependence of specific capacity has been previously observed for RuO2·xH2O, but to the best of our knowledge, this is the first example in an organic system. Surprisingly, the observed capacity is substantially higher than that of state-of-the-art inorganic LIC cathodes and pseudocapacitive electrodes operating at equivalent electrochemical potentials. Furthermore, 225 mAhg -1 (pH=0), 135mAhg -1 (pH=14.7), and 72mAhg -1The high volume (pH=7.3) can be accessed within 33 seconds, demonstrating excellent rate capability. pBTABQ is available at 0.2, 5, and 100mVs. -1 With the increased scanning speed, 320mAhg -1 (Q max , 0.05mVs -1 ) exhibits maximum rate capacity at pH 0 with retention rates of 96%, 90%, and 70% of the maximum capacity, respectively. Alternatively, the 12-electron reduction of pBTABQ yields 389 mAhg -1 The theoretical volume is allocated, and the usefulness of the experimental bulk of pBTABQ at pH 0 is shown as 82%. 2-10Ag -1 Further GCD testing at pH0 using high current density was performed at a rate corresponding to 6-50C (1C = 1 hour discharge) with 200mAhg -1 It releases a larger volume.

[0130] The emergence of high-capacity and redox peaks under acidic and alkaline conditions was analyzed by excitatory studies of the polarization electrode. Firstly, charge accumulation occurs further by the reduction of imines and carbonyls, as evidenced by the decrease in intensity of the XPS signals for O1s(C=O) and N1s(C=N) during polarization (Figure 22). In particular, ion intercalation under strongly acidic conditions occurs almost exclusively by protons, as evidenced by the absence of alkali ions in XPS and elemental mapping (Figure 23). Secondly, the emergence of broad redox peaks suggests local redox states, likely due to weakened electron delocalization by partial protonation or deprotonation of the electrode material under strongly acidic or alkaline conditions. Indeed, the UV-Vis spectra of pBTABQ immersed in acid or base show significantly blue-shifted absorption (Figure 25), indicating more local electronic structure. XPS analysis (Figure 22) shows that proton-bonded electron transfer (PCET) occurs sequentially under acidic conditions, starting with both imines and carbonyls (pH 0, first peak), and then only with carbonyls (pH 0, second peak), while broad reductive enolate formation is dominant under alkaline conditions (pH 14.7). Notably, the proton selectivity for metal cations highlights excellent bulk proton diffusion via the electrode's hydrogen bonding network, leading to superior charge accumulation across the electrode bulk. However, the contribution of PCET appears to be very limited under high-basic conditions (pH > 13) and cannot explain the substantial increase in specific capacity. Instead, substantially more Na + This was observed in polarized pBTABQ under alkaline conditions rather than under neutral conditions (Figure 24), indicating a significant improvement in the intercalation of metal cations into the electrode. This appears to be due to hydrogen-bond-assisted partial deprotonation of the bulk electrode material by hydroxide ions at alkaline pH.

[0131] (Example 4) The following examples describe the charge and discharge capabilities of systems utilizing BTABQ molecules and materials containing pBTABQ.

[0132] The inventors have benefited from the recent development of water-in-salt electrolytes (WiSE) and explored the deep charge-discharge ability of pBTABQ at a larger reduction potential window of 1.5 V. The CV recorded in 17 mol of NaClO4 remains nearly rectangular and discharges a capacity similar to that seen in an aqueous neutral electrolyte with excellent cycle stability over 40,000 cycles (Figure 26). In particular, the EDS map of the polarized pBTABQ electrode in WiSE reveals a significantly larger amount of intercalated Na than that observed in a neutral electrolyte + and indicates a limited PCET contribution. Indeed, the capacitive behavior in CV and the EIS on the extended potential window in WiSE discharge a high charge capacity of 225 mAhg -1 with a 50% increase for neutral conditions. The rate capability study shows ultra-high rate performance with various active material loadings up to a practically relevant value of 6 mg cm -2 (Figure 27). For example, a discharge capacity of more than 100 mAhg -1 can be discharged within 60 seconds. The overview of pBTABQ performance in acidic, alkaline, and WiSE electrolytes emphasizes its superiority over state-of-the-art high-capacity LIC cathodes and high-rate pseudocapacitive electrodes (Figure 28). Materials tested at a potential greater than 2 V vs. Li + / Li with a minimum active material loading of 1.5 mg cm -2 were selected for comparison (MS-Mxene: Ti3C2T x synthesized using molten alkali salts, PHATN: perylene diimide-hexaazatrinaphthylene, NCA, NMCAM, and NMA: Ni-rich analogs of LiNiO2 doped with Al, Mn, Co, and Mg, Ni3BHT: Ni3(benzenehexathiol)). An asymmetric hybrid capacitor fabricated using pBTABQ as the anode and porous activated carbon as the cathode safely discharges 2 V and cycles over 60,000 cycles with a capacity retention rate exceeding 90%. The careful selection of the WiSE electrolyte can further improve the cell voltage to 2.3 V. Overall, the fundamental understanding and design principles of organic pseudocapacitive materials here represent an essential step towards practical, high-rate, high-capacity EES devices.

[0133] (Example 5) The following examples describe the materials and methods used to synthesize materials containing BTABQ molecules and pBTABQ and to show their properties.

[0134] Synthesis of BTABQ: 6 mL of dimethylformamide (DMF, Sigma-Aldrich) was added to a 15 mL pressure tube (ACE Glass, 150 psi) equipped with 28.4 mg of tetraamino-p-benzoquinone (TABQ synthesized using previously reported procedures) and 220 mg of tetrabutylammonium chloride (TBACl, TCI). The tube was capped under ambient conditions, sonicated for 1 minute, and then placed in an oven at 120 °C. After 12 hours, the tube was cooled to room temperature, and the reaction mixture was filtered and washed with DMF until the resulting filtrate became colorless. The resulting black solid was further washed with methanol (Sigma-Aldrich) and dried under air. 15.5 mg of BTABQ was obtained (60% yield). BTABQ is insoluble in common NMR solvents. Solid-state NMR of BTABQ: 174.8 ppm (C=O), 146.4 ppm (C=N), 134.5 ppm / 129.9 ppm (C-N / C-O). Elemental analysis: C 12 H 10 O4N6, found: C, 47.14%; H, 2.84%; N, 26.06%; calculated: C, 47.69%; H, 3.33%; N, 27.81%. MALDI-TOF: [M+H] + : found, 303.9; calculated: 303.1; within the ±1 Da error of the instrument. The crystallinity of BTABQ was characterized by PXRD.

[0135] The synthesis of BTABQ can be scaled up to the gram scale: 80 mL of dimethylformamide (DMF, Sigma-Aldrich) was added to a 250 mL Schlenk tube (ChemGlass) containing 1.07 g of TABQ and 10.3 g of tetrabutylammonium bromide (TBABr, Sigma-Aldrich). The Schlenk tube was sealed under ambient conditions, sonicated for 1 minute, and then placed in a constant temperature oven at 120°C. After 12 hours, the Schlenk tube was cooled to room temperature, and the reaction mixture was filtered and washed with DMF until the resulting filtrate was colorless. The resulting black solid was further washed with methanol (Sigma-Aldrich) and dried under air. 0.4 g of BTABQ was obtained (42% yield).

[0136] Synthesis of pBTABQ: 100 mg of BTABQ was transferred to a glass tube and heated under vacuum at approximately 300°C for 2 days. 85 mg of pBTABQ was obtained as a black solid. Elemental analysis: C 36 H 10 O 10 N 16 Actual values: C, 52.48%; H, 1.44%; N, 26.34%; Calculated values: C, 52.31%; H, 1.22%; N, 27.11%. MALDI-TOF: [M+H] + : Measured value: 827.7; Calculated value: 827.1; [(M-NH3)+H] + Actual value: 810.7; Calculated value: 810.1; Within ±1 Da error of the equipment.

[0137] Electrode preparation: The working electrode was prepared as a slurry by mixing the active material, polyvinylidene fluoride (PVDF), and acetylene black carbon in an 8:1:1 ratio using dimethylformamide, and then measuring 0.3 cm. 2 The electrodes were coated onto carbon fiber paper discs (Fuel Cell Earth). The prepared electrodes were dried in air at 65°C for 3 hours, and then dried overnight under vacuum at 120°C. The dried electrodes had a concentration of 1.5–6 mg / cm³. 2 It has a packing density of .

[0138] An activated carbon counter electrode was prepared as a thin film by repeatedly kneading and rotating a slurry of activated carbon, acetylene black, and PTFE solution in an 8:1:1 ratio with ethanol. The prepared film was dried overnight at 120°C before use.

[0139] Electrolyte preparation: Electrochemical tests under neutral conditions were performed using a 1M aqueous solution containing LiCl, NaCl, MgCl2, and tetraethylammonium chloride (TEACl) in deionized water. Detailed studies aimed at investigating the role of water were performed using a 1M solution containing NaClO4 and tetraethylammonium tetrafluoroborate (TEABF4) in pure water, anhydrous acetonitrile (MeCN), and solution mixtures containing 1% and 5% water in MeCN.

[0140] The role of pH in electrochemical performance was investigated using electrolytes with pH values ​​ranging from 0 to 14.7. Electrolytes with intermediate pH values ​​of 2 to 13 were buffered, while strongly acidic and basic solutions were unbuffered. Equivalent ionic strength was maintained using 1 M NaCl, but the pH of the buffer was adjusted using HCl and NaOH. A description of the electrolytes and their components is shown in Table 1. [Table 1]

[0141] Deep charge-discharge tests in water-in-salt electrolyte (WiSE) were performed using a 3-electrode structure with 17 m (molar concentration) of NaClO4. Two electrode devices were fabricated using WiSE containing 12.5 m of LiNO3 in a 1:1 weight ratio of water and 1,5-pentanediol.

[0142] In-house powder X-ray diffraction (PXRD) patterns were recorded using a Bruker Advance II diffractometer equipped with θ / 2θ reflection geometry and Ni-filtered CuKα radiation (Kα1=1.5406 Å, Kα2=1.5444 Å, Kα2 / Kα1=0.5). Tube voltage and current were 40 kV and 40 mA, respectively. PXRD samples were prepared by placing thin layers of appropriate material on a zero-background silicon crystal plate.

[0143] For cRED data acquisition, processing, and structural analysis of BTABQ, the crystals were dispersed in ethanol and sonicated for 5 minutes. Subsequently, droplets of the suspension were transferred onto a copper grid with a carbon film. cRED data were acquired using a 200kV JEOL JEM-2100 transmission electron microscope equipped with a quad-hybrid pixel detector (Timepix, 512×512 pixels, pixel size: 55μm, Amsterdam Sci.Ins.). Prior to acquisition, the sample was cooled to 96K using a Gatan cryotransfer tomography holder. During acquisition, the goniometer was continuously rotated while simultaneously capturing limited-field electron diffraction (ED) patterns from the crystal using Instamatic software. To maintain a balance between electron diffraction intensity and resolution, all ED patterns were recorded with an exposure time of 0.5 s and a spot size of 3. The 3D reciprocal grid was reconstructed using the REDp software, which proved very useful in determining and obtaining the reflection conditions.

[0144] For the structural analysis of BTABQ, five orthorhombic crystals were identified using the mean lattice constants a=Å, b=Å, and c=Å in the space group (reflection conditions: hk0, h+k=2n, h0l, h=2n, 0k0, k=2n). The X-ray crystallography software package XDS was used for data processing to estimate the aggregate diffraction intensity. Subsequently, XSCALE was applied for data integration to improve completeness, achieving 88.9% completeness through the integration of the five datasets. The SHELX software package was used for structural analysis, and SHELXT was used for structural analysis. Measuring the resolution of these cRED datasets to 0.625 Å allowed all non-hydrogen atom positions in BTABQ to be directly determined by the ab initial method. SHELXL was used for structural refinement, applied to all atoms of the electron scattering factor. Atomic displacement parameters (ADP) for all skeletal atoms were anisotropically refined.

[0145] High-resolution synchrotron PXRD data were collected at 100K at beamline 11-BM of the Advanced Photon Source (APS) at Argonne National Laboratory, using Debye-Scherrer geometry and an average calibration wavelength of 0.458111 Å.

[0146] Pawley refinement of BTABQ synchrotron data was performed using TOPAS Academic (version 6). The refined lattice constants of BTABQ at 100K are R wp =5.828, R exp =5.248, R p For the space group P21 / c with =4.667 and GoF=1.11, a=4.8923(1)Å, b=11.2897(3)Å, c=9.9041(4)Å, and β=101.67°.

[0147] N2 adsorption isotherms were measured by volumetric method using a Micromeritics ASAP 2020 Plus gas sorption analyzer. Oven-dried sample tubes equipped with TranSeal® (Micromeritics) were degassed and weighed. The sample was transferred to the sample tube and then sealed with TranSeal®. The sample was left under high dynamic vacuum (<10°C) for 24 hours before analysis. -4 The N2 isotherm was activated at 100°C under mbar conditions. The N2 isotherm was measured using a liquid nitrogen bath at 77K. Ultra-high purity grade (99.999% purity) N2, oil-free valves, and gas regulators were used for all free-space corrections and measurements. Conformance to the Brunauer-Emmett-Teller (BET) formula met the published consistency criteria.

[0148] Thermogravimetric analysis (TGA) was performed on a platinum pan from room temperature to 700°C at a heating rate of 2.0°C / min under a flow of air or N2 gas at 5 mL / min using a TA Instruments Q500 Thermogravimetric Analyzer.

[0149] Elemental analysis was performed by Robertson Microlit Laboratories, Ledgewood, and New Jersey.

[0150] X-ray photoelectron spectroscopy (XPS) measurements were performed at MIT MRSEC (formerly the Center for Materials Science and Engineering, i.e., CMSE) using a Physical Electronics PHI Versaprobe II X-ray photoelectron spectrometer equipped with a monochromatic Al anode X-ray source. The main chamber pressure was 10 -10The sample was in the Toll range. MOF powder samples were completely coated and pressed onto copper tape. Measurement spectra were collected from binding energy (BE) 0–1100 eV with a resolution of 0.8 eV. High-resolution spectra in the C1s, N1s, and M2p regions were collected with a resolution of 0.1 eV. BE calibration was performed by shifting the undefined carbon C1s peak to 284.8 eV. If the MOF sample contained a larger amount of carbon, the C1s spectrum was analyzed before BE calibration to find the undefined carbon C1s peak. A Gauss-Lorentz production function with a 30% Lorentz component was used linearly during fitting, and it is generally used for C1s.

[0151] Scanning electron microscopy (SEM) was performed at MIT MRSEC (formerly the Center for Materials Science and Engineering, i.e., CMSE) using a Zeiss Merlin high-resolution scanning electron microscope equipped with an InLens detector, at a working voltage of 3 or 4 kV.

[0152] MALDI-TOF mass spectrometry was performed using a high-resolution Bruker Autoflex LRF Speed ​​mass spectrometer in positive linear mode. Dislanol was used as the matrix. Powdered samples were mixed with dislanol using a mortar and pestle, and the mixture was compressed into pellets for measurement. No internal standards were used, and therefore the mass accuracy is ±1 Da.

[0153] Cryo-HRTEM images were obtained using the automated cryo-electron microscopy facility at MIT.nano with a Talos Arctica G2 microscope operated with a Falcon3EC direct electron detector at an accelerating voltage of 200kV. Samples were prepared by sonicating powder in isopropanol for approximately 5 seconds. Specimens were prepared by drop-casting the sonicated samples onto a C-flat® Cu grid with carbon perforated for Cryo-EM. Prior to image acquisition (standard low-dose imaging protocol), focusing was performed adjacent to the imaged region to minimize beam exposure, and all image acquisitions were performed using an EPU with an exposure time of 1 s. Raw HRTEM data were analyzed using Gatan Microscopy Suite software (GMS3).

[0154] Diffuse reflection infrared Fourier transform spectroscopy (DRIFTS) was performed on a Bruker Tensor 37 (MIR source and KBr beam splitter) with a mercury-cadmium tellurium (LN2-cooled MCT) detector utilizing DiffusIR® accessories (Pike Technologies). A sealed environmental chamber with a ZnSe window (Pike Technologies) was used to ensure air-free measurements. Samples were ground in air using dry KBr (99.9%, Pike Technologies) in a mortar and pestle to produce 0.5–1 wt% mixtures. Data were collected at 4 cm². -1 Resolution of 4000-600cm -1 The average was calculated over 64 scans. Each Kubelka-Munk function transform DRIFTS spectrum was measured at 4000 cm⁻¹. -1 The F(R) DRIFTS value was set to 4000cm. -1 The DRUV-vis-NIR data was normalized by matching it with the DRUV-vis-NIR value of F(R) for the same sample.

[0155] Diffuse reflectance UV-Vis-NIR spectra (DRUV-Vis-NIR) from 200 to 2500 nm were collected under ambient conditions at a scanning speed of 600 nm / min using a Cary 5000i spectrophotometer equipped with a UV-Vis DiffusIR accessory (Pike Technologies). KBr baseline and zero background corrections were collected prior to sample measurement. Samples were prepared as described above for DRIFTS measurements. For Tauc plots and optical bandgap measurements, UV-Vis-NIR spectra were manually stitched with DRIFTS spectra obtained for the same samples.

[0156] The Raman spectra of solid samples were measured using a Renishaw Invia reflection-Raman confocal microscope under a 532 nm excitation laser, with the laser power not exceeding 5% of the total power.

[0157] Room temperature conductivity measurements were performed at 294 K in ambient atmosphere on pressurized pellets using the four-probe setup described earlier. For each sample, the conductivity values ​​were averaged across at least three devices.

[0158] Electron paramagnetic resonance (EPR) spectroscopy measurements were performed on activated samples packed under nitrogen in a septum-sealed quartz tube using a Bruker EMX spectrometer equipped with an ER 4199HS cavity and a Gunn diode microwave source at approximately 5 K, with a microwave frequency of 9.37 GHz, power of 0.100 mW, and attenuation of 33.0 dB. Measurements were performed in vertical mode. Pure MOF and CCP powder samples were used for the measurements.

[0159] In-situ wide-angle X-ray scattering (WAXS) measurements were performed at the soft-material interface beamline (12-ID) of the National Synchrotron Light Source II (NSLS-II) at Brookhaven National Laboratory, with a beam energy of 16.1 keV and a beam size of 200 × 20 μm. A coin cell was connected to a Princeton Applied Research Potentiostat (PARSTAT2273) for in-situ bias control via a metal wire. A domestically produced 3D-printed holder was used to load the coin cell sample onto the transmission WAXS research sample stage, ensuring the cell remained within the beamline. Scattering data was collected in vacuum using a PILATUS3 300kW detector (Dectris, Switzerland) consisting of a 1475 × 195 array with 0.172 mm square pixels. To obtain a wide range of wave vector shifts (q), a series of 2D diffraction patterns were collected by rotating the detector in an arc with a sample-detector distance of 275 mm. The scattering patterns from each detector angle were stitched together using custom software and then reduced to a 1D scattering intensity vs. q curve by circumferential averaging. The in situ cell for WAXS was designed by machining an industrial CR 2032 coin cell. Specifically, a 3 mm diameter hole was drilled into the upper and lower casings of the coin cell. The hole was covered with a piece of Kapton tape and sealed with epoxy to promote X-ray transmission and prevent electrolyte leakage. Similar holes were fabricated in the separator and porous carbon counter electrode. All cell components were carefully stacked and positioned to ensure seamless transmission of the X-ray beam through the BTABQ pellet. The fabricated cells were tested for their electrochemical properties using cyclic voltammetry before being loaded into the WAXS chamber. The cells were tested at their corresponding residual potentials and then reversibly polarized to -0.9 V vs. OCP.

[0160] Excitu high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images and energy-dispersive spectroscopy elemental mappings were collected at MIT MRSEC (formerly the Center for Materials Science and Engineering, i.e., CMSE) on a JEOL 2010 FEG analytical electron microscope equipped with an Oxford Instrument ULTIM MAX detector. Specimens were prepared by drop-casting polarized samples onto a Cu grid.

[0161] Electrochemical Characterization Method: The synthetic material was initially tested in a three-electrode supercapacitor structure using porous activated carbon (YP50) as the counter, silver wire as the reference electrode, and a 25 μm thick cellulose sheet as the separator. Excess weight porous activated carbon electrodes were used to accommodate the charge and ensure a distinct response from the working electrode. Cell components were assembled using a custom-made T-shaped Swagelok-type cell. Aqueous, organic, or aqueous / organic mixed solutions of various metal salts were used as electrolytes. The cells were assembled in a ventilated hood and allowed to stand for 12 hours before electrochemical testing.

[0162] All electrochemical measurements were performed using a Biologic VSP-300 potentiostat controlled by the EC-Lab software. EIS measurements were performed using a multisynusoid signal with an amplitude of 10mV over a wide frequency range of 10mHz to 200kHz. Specific gravity capacity (C) g ) to, Equation 1:

number

[0163] The dynamics of the electrochemical process were analyzed using the exponential law shown in Equation 2.

number

[0164] By plotting log(i) versus log(υ), it became possible to measure b as the slope of the fitting. Following this approach, b values ​​were evaluated at various potentials on the CV over a series of scanning speeds using neutral, acidic, and basic electrolytes.

[0165] Calculation of theoretical capacity: The theoretical capacity of the material is calculated using Equation 3:

number

[0166] For BTABQ, the theoretical capacity is 355 mAhg, based on the redox process shown in Figure 29. -1 This was calculated (n=4).

[0167] For pBTABQ, the theoretical capacity is 389 mAhg based on the redox process shown in Figure 30. -1 This was calculated (n=12).

[0168] While several embodiments of the present invention have been described and illustrated herein, those skilled in the art will readily conceive of various other means and / or structures to perform the function and / or obtain one or more of the results and / or benefits described herein, and each such change and / or modification will be considered within the scope of the present invention. More generally, those skilled in the art will understand that all parameters, dimensions, materials, and structures described herein are illustrative, and that actual parameters, dimensions, materials, and / or structures will depend on the specific application or application in which the teachings of the present invention are used. Those skilled in the art will recognize many equivalents to the specific embodiments of the present invention described herein, or can verify them by means of routine experimentation alone. Therefore, it should be understood that the embodiments described herein are merely illustrative, and the present invention can be carried out in ways other than those specifically described and claimed, within the scope of the appended claims and equivalents thereof. The present invention covers each of the individual features, systems, articles, materials, kits, and / or methods described herein. Furthermore, any combination of two or more such features, systems, articles, materials, kits, and / or methods is also included in the scope of the present invention, provided that such features, systems, articles, materials, kits, and / or methods are not contradictory to each other.

[0169] All definitions defined and used herein should be understood to take precedence over dictionary definitions, definitions in documents incorporated herein by reference, and / or the ordinary meanings of the terms defined.

[0170] Where used herein and in the claims, the indefinite articles "a" and "an" should be understood to mean "at least one" unless explicitly stated otherwise.

[0171] The phrase "and / or" as used herein and in the claims should be understood to mean "either or both" of the elements thus combined, i.e., elements that exist conjugate in some cases and disjunct in others. Many of the elements listed in "and / or," i.e., "one or more" of the elements thus combined, should be interpreted similarly. In addition to the elements specifically identified by the clause "and / or," other elements may exist as needed, whether related to or unrelated to those specifically identified elements. Thus, as an example, though not limited to this, when the expression "A and / or B" is used in combination with a non-exclusive word such as "comprising," in one embodiment it may refer to A only (including elements other than B as needed), in another embodiment it may refer to B only (including elements other than A as needed), in yet another embodiment it may refer to both A and B (including other elements as needed), and so on.

[0172] Where used herein and in the claims, “or” should be understood to have the same meaning as “and / or” as defined above. For example, when dividing items in a list, “or” or “and / or” should be interpreted as inclusive, that is, including not only at least one of the list of numbers or elements, but more than one of the list of numbers or elements, and there may be additional items not on the list as needed. Only terms that are explicitly indicated as “only one of…” or “exactly one of…” or, as used in the claims, “consisting of…” would mean including exactly one of a number of elements or elements of a list. In general, where used herein, the term “or” should be interpreted as indicating an exclusive choice (i.e., “one or the other, but not both”) only when preceded by an exclusive term such as “either,” “one of…” or “only one of…” or “exactly one of…” When used in patent claims, "essentially consisting of..." has the usual meaning as it is used in the field of patent law.

[0173] When used herein and in the claims, the phrase “at least one” with respect to a list of one or more elements should be understood to mean at least one element selected from any one or more elements in the list of elements, but not all of each element specifically listed in the list of elements must be included in at least one instance, nor is any combination of elements in the list of elements excluded. This definition also allows for the presence of elements other than those specifically identified in the list of elements referred to by the phrase “at least one,” as necessary, regardless of whether or not they are related to those specifically identified elements. Thus, as an example, though not limited to this, "at least one of A and B" (or "at least one of A or B" is equivalent thereto, or "at least one of A and / or B" is equivalent thereto) can, in one embodiment, refer to at least one A, which may be more than one as needed, in the absence of B (and may include elements other than B as needed); in another embodiment, refer to at least one B, which may be more than one as needed, in the absence of A (and may include elements other than A as needed); in yet another embodiment, refer to at least one A, which may be more than one as needed, and at least one B, which may be more than one as needed (and may include other elements as needed), and so on.

[0174] Furthermore, unless otherwise explicitly stated, in any method claimed herein that includes more than one step or action, the order of the steps or actions of the method is not necessarily limited to the order in which the steps or actions of the method are cited.

[0175] In the claims and the above specification, transitional phrases such as “include,” “equip,” “carry,” “have,” “include,” “related,” “hold,” and “constitute” should all be understood as unrestrictive; that is, they include, but are not limited to. Only the transitional phrases “consist of…” and “substantially consist of…” are closed or semi-closed transitional phrases, respectively, as described in Section 2111.03 of the U.S. Patent and Trademark Office's Patent Examination Procedure Manual. The present invention provides, for example, the following items: (Item 1) Structure below: [ka] A composition comprising the bis-tetraamino-benzoquinone molecule, and / or its tautomers, oligomers, and / or polymers. (Item 2) Structure below: [ka] An electrode comprising a bis-tetraamino-benzoquinone molecule, and / or its tautomers, oligomers, and / or polymers. (Item 3) The electrode according to item 2, comprising multiple bis-tetraamino-benzoquinone molecules, and / or tautomers, oligomers, and / or polymers thereof. (Item 4) The electrode according to item 3, wherein at least a portion of the plurality of bis-tetraamino-benzoquinone molecules, and / or their tautomers, oligomers, and / or polymers, interact in a planar and / or two-dimensional structure via hydrogen bonding. (Item 5) The electrode according to any one of items 3 and 4, wherein at least a portion of the plurality of bis-tetraamino-benzoquinone molecules, and / or their tautomers, oligomers, and / or polymers, interact in a three-dimensional stacked structure via π-π interactions. (Item 6) The electrode is 10 -7 An electrode according to any one of items 2 to 5, having conductivity greater than or equal to S / cm. (Item 7) The electrode according to any one of items 2 to 6, wherein the electrode has a specific capacity greater than or equal to 300 F / g. (Item 8) The electrode described in item 7, wherein the specific capacitance is measured at a scanning speed of 0.2 mV / s. (Item 9) The electrode according to any one of items 2 to 7, wherein the electrode has a cycle performance of more than or equal to 20,000 cycles. (Item 10) The electrode described in item 9, wherein the cycle performance is measured at a scanning speed of 30 mV / s. (Item 11) First electrode, The second electrode, and Contains electrolytes, An electrochemical cell in which the first electrode and / or the second electrode are electrodes described in any one of items 2 to 10. (Item 12) The electrochemical cell according to item 11, wherein the electrolyte is a liquid electrolyte having a pH greater than or equal to 0 and less than or equal to 2. (Item 13) The electrochemical cell according to either item 11 or 12, wherein the electrolyte is a liquid electrolyte having a pH greater than or equal to 12 and less than or equal to 15. (Item 14) The active material includes a condensed aromatic system containing carbon atoms, hydrogen atoms, and multiple heteroatoms that replace each carbon atom, An electrochemically active charge storage material in which the ratio of carbon atoms to heteroatoms is greater than 1 and less than 2, and the plurality of heteroatoms include N, O, S, and / or Se. (Item 15) The active material includes a condensed aromatic system containing carbon atoms, hydrogen atoms, and multiple heteroatoms that replace each carbon atom, An electrochemically active charge-storing material in which at least a portion of the condensed aromatic system is in a planar and / or two-dimensional structure via several hydrogen bonding interactions, wherein the number of hydrogen bonding interactions is greater than or equal to 0.3 and less than or equal to 1 per mole of carbon atoms. (Item 16) The electrochemically active charge storage material comprises an active material, the active material comprising a condensed aromatic system comprising carbon, hydrogen, and one or more heteroatoms replacing carbon atoms, The electrochemically active charge storage material has a charge capacity greater than or equal to 100 mAh per gram of active material, and / or A charge storage device wherein the electrochemically active charge storage material has a charge capacity greater than or equal to 50 mAh per gram of electrochemically active charge storage material. (Item 17) The charge storage device according to item 16, wherein the charge capacity is discharged at a charge and / or discharge rate of less than 60 seconds. (Item 18) An electrochemically active charge storage material comprising an active material, wherein the active material comprises a condensed aromatic system containing carbon, hydrogen, and one or more heteroatoms replacing carbon atoms, The electrochemically active charge-accumulating material is placed in the electrolyte. A charge storage device wherein the electrochemically active charge storage material has a charge capacity that is at least 50% greater when the pH value of the electrolyte is greater than 2 and less than 12 compared to when the pH value of the electrolyte is greater than 2 and less than 12. (Item 19) An electrochemically active charge storage material comprising an active material, wherein the active material comprises a condensed aromatic system containing carbon, hydrogen, and one or more heteroatoms replacing carbon atoms, The electrochemically active charge storage material is 2.0V vs. Li + A charge storage device that releases at least 90% of its charge capacity at a voltage higher than that of a lithium standard reference electrode. (Item 20) An electrochemically active charge storage material comprising an active material, wherein the active material comprises a condensed aromatic system comprising carbon atoms, hydrogen atoms, and a plurality of heteroatoms that replace carbon atoms, A charge storage device in which the molar ratio of electrons stored as charge per mole of heteroatoms is greater than or equal to 0.3 and less than or equal to 0.6. (Item 21) An electrochemically active charge storage material comprising an active material, wherein the active material comprises an organic material, The active material has a solubility of less than or equal to 1 millimoles per liter of solvent at ambient temperature and atmospheric pressure. A charge storage device wherein the electrochemically active charge storage material has a charge capacity retention rate greater than or equal to 85% after at least 20,000 cycles. (Item 22) A charge storage device according to any one of items 16 to 21, wherein the charge storage device is a capacitor. (Item 23) The charge storage device according to item 22, wherein the capacitor is a supercapacitor.

Claims

1. Structure below: 【Chemistry 11】 A composition comprising the bis-tetraamino-benzoquinone molecule, and / or its tautomers, oligomers, and / or polymers.

2. Structure below: 【Chemistry 12】 An electrode comprising a bis-tetraamino-benzoquinone molecule, and / or its tautomers, oligomers, and / or polymers.

3. The electrode according to claim 2, comprising a plurality of bis-tetraamino-benzoquinone molecules, and / or tautomers, oligomers, and / or polymers thereof.

4. The electrode according to claim 3, wherein at least a portion of the plurality of bis-tetraamino-benzoquinone molecules, and / or their tautomers, oligomers, and / or polymers, interact in a planar and / or two-dimensional structure via hydrogen bonding.

5. The electrode according to any one of claims 3 and 4, wherein at least a portion of the plurality of bis-tetraamino-benzoquinone molecules, and / or their tautomers, oligomers, and / or polymers, interact in a three-dimensional stacked structure via π-π interactions.

6. The electrode is 10 －７ The electrode according to any one of claims 2 to 5, having conductivity greater than or equal to S / cm.

7. The electrode according to any one of claims 2 to 6, wherein the electrode has a specific capacity greater than or equal to 300 F / g.

8. The electrode according to claim 7, wherein the specific capacitance is measured at a scanning speed of 0.2 mV / s.

9. The electrode according to any one of claims 2 to 7, wherein the electrode has a cycle performance greater than or equal to 20,000 cycles.

10. The electrode according to claim 9, wherein the cycle performance is measured at a scanning speed of 30 mV / s.

11. First electrode, The second electrode, and Contains electrolytes, An electrochemical cell in which the first electrode and / or the second electrode is the electrode according to any one of claims 2 to 10.

12. The electrochemical cell according to claim 11, wherein the electrolyte is a liquid electrolyte having a pH greater than or equal to 0 and less than or equal to 2.

13. The electrochemical cell according to claim 11, wherein the electrolyte is a liquid electrolyte having a pH greater than or equal to 12 and less than or equal to 15.

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