Metal-organic structures for supercapacitor electrodes

Abstract

Metal-organic frameworks, supercapacitor electrodes, and supercapacitors are generally provided. Some metal-organic frameworks described herein may be suitable for use in supercapacitor electrodes, some supercapacitor electrodes described herein may include a metal-organic framework described herein, and some supercapacitors described herein may include a supercapacitor electrode described herein.

Description

[Technical Field]

[0001] Related applications This application claims priority to U.S. Provisional Application No. 62 / 908,297, filed on 30 September 2019 under 35 U.S.C. § 119(e) and titled "Metal-Organic Frameworks for Supercapacitor Electrodes," which is incorporated herein by reference in its entirety for all purposes.

[0002] Technical field Metal-organic structures suitable for use as supercapacitor electrodes, supercapacitor electrodes containing metal-organic structures, supercapacitors, and related articles and compositions are generally provided. [Background technology]

[0003] background Supercapacitors are increasingly being used in more applications due to their significantly higher power output capacity compared to batteries. Batteries, on the other hand, excel in high energy capacity. For this reason, one of the challenges facing current technological research and development is designing cells that can exhibit both the high power density of supercapacitors and the high energy density of batteries, and therefore, new electrodes that possess both high power density and high energy density are needed. [Overview of the project] [Means for solving the problem]

[0004] overview This document provides a general description of metal-organic structures, supercapacitor electrodes, and supercapacitors.

[0005] In some embodiments, a supercapacitor electrode is provided. The supercapacitor electrode comprises a metal-organic structure containing multiple metal ions coordinated by multiple ligands. The multiple ligands include ligands containing two or more sulfur donor atoms. The metal ions are coordinated by the sulfur donor atoms, thereby coordinating the ligands containing sulfur donor atoms.

[0006] In some embodiments, the supercapacitor electrode includes a metal-organic structure containing multiple metal ions coordinated by multiple ligands. The metal-organic structure is configured to interact with the second set of ions such that the second set of ions intercalates and / or is absorbed into the metal-organic structure. The metal-organic structure is configured so that at least some of the metal ions undergo redox reactions during charging and discharging of the supercapacitor electrode.

[0007] In some embodiments, a method is provided. The method involves performing a redox reaction in a metal-organic structure containing multiple metal ions coordinated by multiple ligands, thereby intercalating a second set of ions into the metal-organic structure. Together, the second set of ions and the metal-organic structure have a neutral charge.

[0008] In some embodiments, a metal-organic structure is provided. The metal-organic structure comprises multiple metal ions coordinated by multiple ligands. The metal ions include nickel ions, cobalt ions, iron ions, platinum ions, and / or palladium ions. The multiple ligands comprise ligands containing two or more sulfur donor atoms. The metal ions are coordinated by the sulfur donor atoms, thereby comprising ligands containing sulfur donor atoms. The metal-organic structure comprises multiple pores having an average pore diameter greater than or equal to 0.3 nm and less than or equal to 1 nm.

[0009] In some embodiments, a supercapacitor is provided. The supercapacitor includes a first electrode comprising a first metal-organic structure and a second electrode comprising a second metal-organic structure. Each metal-organic structure comprises multiple metal ions coordinated by multiple ligands. The second metal-organic structure is different from the first metal-organic structure.

[0010] 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. In the event that this specification and any documents incorporated by reference contain any conflicting and / or contradictory disclosures, this specification shall prevail.

[0011] Non-limiting embodiments of the present invention will be described by reference with the accompanying schematic and not-to-scale drawings. In the drawings, each of the identical or substantially identical components illustrated is typically represented by a singular noun. For clarity, not all components are labeled in all drawings, and not all components of each embodiment of the present invention are shown where it is not necessarily required for the drawings to convey the invention to those skilled in the art. In embodiments of the present invention, for example, the following items are provided. (Item 1) A supercapacitor electrode comprising a metal-organic structure containing multiple metal ions coordinated by multiple ligands, The plurality of ligands include ligands containing two or more sulfur donor atoms, The aforementioned metal ion is coordinated to the aforementioned sulfur donor atom by the aforementioned sulfur donor atom, the ligand containing the sulfur donor atom, Supercapacitor electrodes. (Item 2) A supercapacitor electrode comprising a metal-organic structure containing multiple metal ions coordinated by multiple ligands, The metal-organic structure is configured to interact with the second plurality of ions such that the second plurality of ions intercalate and / or are absorbed into the metal-organic structure. The metal-organic structure is configured such that at least a portion of the metal ions undergo a redox reaction during the charging and discharging of the supercapacitor electrode. Supercapacitor electrodes. (Item 3) The process of carrying out redox reactions within a metal-organic structure containing multiple metal ions coordinated by multiple ligands, and Intercalating a second plurality of ions into the metal-organic structure such that the second plurality of ions and the metal-organic structure together have a neutral charge. Methods that include... (Item 4) A metal-organic structure containing multiple metal ions coordinated by multiple ligands, The aforementioned metal ions include nickel ions, cobalt ions, iron ions, platinum ions, and / or palladium ions. The plurality of ligands include ligands containing two or more sulfur donor atoms, The aforementioned metal ion is coordinated to the aforementioned sulfur donor atom by the aforementioned sulfur donor atom, and the ligand containing the aforementioned sulfur donor atom is coordinated to the aforementioned sulfur donor atom. Metal-organic structures. (Item 5) A first electrode comprising a first metal-organic structure, A second electrode containing a second metal-organic structure and A supercapacitor including, Each metal-organic structure contains multiple metal ions coordinated with multiple ligands. The second metal-organic structure is different from the first metal-organic structure. Supercapacitor. (Item 6) A supercapacitor, supercapacitor electrode, metal-organic structure, or method according to any of the above items, wherein the plurality of metal ions include nickel ions and the plurality of ligands include benzene hexathiol ligands. (Item 7) The aforementioned metal-organic structure has the following structure:

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[0012] [Figure 1] Figure 1 shows one non-limiting embodiment of a metal-organic structure according to some embodiments. [Figure 2] Figure 2 shows one non-limiting embodiment of a metal-organic structure comprising multiple two-dimensional sheets, according to some embodiments. [Figure 3] Figure 3 shows one non-limiting embodiment of the upper surface of a metal-organic structure containing multiple pores, according to some embodiments. [Figure 4] Figure 4 shows one non-limiting embodiment of the side of such a two-dimensional sheet within a metal-organic structure, according to some embodiments. [Figure 5] Figure 5 shows one non-limiting embodiment of a method for intercalating ions within a metal-organic structure between two two-dimensional sheets, according to some embodiments. [Figure 6] Figure 6 shows one non-limiting embodiment of a method for absorbing ions into multiple pores within a metal-organic structure, according to some embodiments. [Figure 7] Figure 7 shows one non-limiting embodiment of a supercapacitor electrode including a metal-organic structure, according to some embodiments. [Figure 8] Figure 8 shows one non-limiting embodiment of a supercapacitor including electrodes containing a metal-organic structure, according to some embodiments. [Figure 9A]Figure 9A shows one non-limiting embodiment of a structure including a metal-organic structure, according to some embodiments. [Figure 9B] Figure 9B shows the cyclic voltammetry (CV) curve of a Cu3BHT1 electrode in an aqueous LiCl electrolyte according to some embodiments. [Figure 9C] Figure 9C shows constant current charge-discharge sweeping for a metal-organic structure according to some embodiments. [Figure 10] Figure 10 shows cyclic voltammetry curves for metal-organic structures according to some embodiments. [Figure 11A] Figure 11A shows electrochemical impedance spectroscopy (EIS) Nyquist plots collected for the Cu3BHT1 electrode in some embodiments. [Figure 11B] Figure 11B shows the powder X-ray diffraction pattern of Cu3BHT1 according to some embodiments. [Figure 12] Figure 12 shows cyclic voltammetry curves for a Cu3BHT1 electrode in the presence of an electrolyte containing acetonitrile and LiPF6, according to some embodiments. [Figure 13A] Figure 13A shows a schematic diagram of the Ni3BHT1 structure according to some embodiments. [Figure 13B] Figure 13B shows the cyclic voltammetry curve obtained at 2 mV / sec for a metal-organic structure according to some embodiments. [Figure 13C] Figure 13C shows the specific capacitance as a function of scan speed for a metal-organic structure according to some embodiments. [Figure 14A] Figures 14A-14C show cyclic voltammetry curves for Ni3BHT1 in electrolytes containing acetonitrile and LiPF6 at various scan speeds and potential windows according to some embodiments. [Figure 14B-C] Figures 14A-14C show cyclic voltammetry curves for Ni3BHT1 in electrolytes containing acetonitrile and LiPF6 at various scan speeds and potential windows according to some embodiments. [Figure 14D] Figure 14D shows the specific capacitance as a function of scan speed for a metal-organic structure according to some embodiments. [Figure 15] Figure 15 shows the cyclic voltammetry curve of Ni3BHT1 in electrolytes containing acetonitrile and NaPF6, performed at a scan rate of 20 mV / sec according to some embodiments. [Figure 16] Figure 16 shows cyclic voltammetry curves for Ni3BHT1 in electrolytes containing ethylene carbonate, dimethyl carbonate, and LiPF6, performed at a scan rate of 20 mV / sec according to some embodiments. [Figure 17A] Figures 17A to 17D show cyclic voltammetry curves for Ni3BHT1 in electrolytes containing acetonitrile and salts, according to some embodiments. [Figure 17B-C] Figures 17A to 17D show cyclic voltammetry curves for Ni3BHT1 in electrolytes containing acetonitrile and salts, according to some embodiments. [Figure 17D] Figures 17A to 17D show cyclic voltammetry curves for Ni3BHT1 in electrolytes containing acetonitrile and salts, according to some embodiments. [Figure 18A] Figures 18A and 18B show cyclic voltammetry curves for Ni3BHT1 according to some embodiments. [Figure 18B] Figures 18A and 18B show cyclic voltammetry curves for Ni3BHT1 according to some embodiments. [Figure 19A] Figure 19A shows the cyclic voltammetry curve for a supercapacitor measured at 10 mV / s in some embodiments. [Figure 19B] Figure 19B shows a constant current charge-discharge sweep for a supercapacitor according to one embodiment. [Figure 19C] Figure 19C shows the cyclic voltammetry curve for a supercapacitor at 10 mV / s in some embodiments. [Figure 19D] Figure 19D shows the specific capacitance of a supercapacitor as a function of time when cycled at 2A / g at voltages between 0V and 2.5V, according to some embodiments. [Figure 20A] Figure 20A shows a schematic diagram of a method for synthesizing benzene hexathiol ligands according to some embodiments. [Figure 20B] Figure 20B shows a schematic diagram of a method for synthesizing a metal-organic structure from a benzene hexathiol ligand and a metal chloride to form a metal-organic structure containing a metal ion from a metal chloride coordinated by a benzene hexathiol ligand, according to some embodiments. [Figure 21] Figure 21 shows the thermogravimetric response of Ni3BHT1 according to some embodiments. [Figure 22] Figure 22 shows powder X-ray diffraction patterns according to some embodiments. [Figure 23A] Figures 23A and 23B show diagrams of simulated structures with respect to Ni3BHT1 according to some embodiments. [Figure 23B] Figures 23A and 23B show diagrams of simulated structures with respect to Ni3BHT1 according to some embodiments. [Figure 24] Figure 24 shows the diffraction pattern of a selected region with respect to Ni3BHT1 according to some embodiments. [Figure 25A] Figures 25A and 25B show the diffraction patterns of a selected region simulated with respect to Ni3BHT1 according to some embodiments. [Figure 25B] Figures 25A and 25B show the diffraction patterns of a selected region simulated with respect to Ni3BHT1 according to some embodiments. [Figure 26] Figure 26 shows the structures of Ni3BHT1 and Ni3BHT2 according to some embodiments. [Figure 27] Figure 27 shows scanning electron microscope images of Ni3BHT1 according to some embodiments. [Figure 28]Figure 28 shows gas sorption isotherms for Ni3BHT1 obtained using N2 as the probe gas in some embodiments. [Figure 29] Figure 29 shows the variable temperature conductivity of compressed Ni3BHT1 pellets according to some embodiments. [Figure 30] Figure 30 shows the cyclic voltammetry curve at a scan speed of 5 mV / sec when increasing the reduction potential window from 1.0 to 1.7 V in some embodiments. [Figure 31A] Figures 31A and 31B show cyclic voltammetry curves for Ni3BHT1 in 1M LiPF6 / MeCN electrolyte using a 3-electrode cell setup and low scan speed according to some embodiments. [Figure 31B] Figures 31A and 31B show cyclic voltammetry curves for Ni3BHT1 in 1M LiPF6 / MeCN electrolyte using a 3-electrode cell setup and low scan speed according to some embodiments. [Figure 32] Figure 32 shows the cyclic voltammetry curve for Ni3BHT1 in a 1M LiPF6 / MeCN electrolyte, using a 3-electrode cell setup and a scan rate of 5 mV / sec, according to one embodiment. [Figure 33] Figure 33 shows cyclic voltammetry curves for a range of scan speeds between 7 and 28 mV / s across a 1.7 V potential window, according to some embodiments. [Figure 34] Figure 34 is a plot showing current versus scan speed in some embodiments. [Figure 35] Figure 35 is a plot showing the specific discharge capacity in some embodiments. [Figure 36] Figure 36 is a plot showing the capacitance retention rate under iterative cycling at a scan rate of 30 mV / s over 8,000 cycles, according to some embodiments. [Figure 37]Figure 37 is a plot showing the cycling stability of Ni3BHT1 over 2,000 cyclic voltammetry cycles in a 3-electrode setup using a 1.7V potential window and a scan rate of 30mV / sec, according to some embodiments. [Figure 38] Figure 38 is a plot of the impedance obtained for the Ni3BHT1 electrode at frequencies between 10 mHz and 200 kHz, for some embodiments, between a hypothetical and actual element. [Figure 39] Figure 39 is a plot showing the cyclic voltammetry curve at a scan speed of 5 mV / sec according to one embodiment. [Figure 40] Figure 40 shows the weight-specific volume according to some embodiments. [Figure 41A] Figure 41A is a plot showing the Nyquist impedance spectrum of Ni3BHT1 according to some embodiments. [Figure 41B] Figure 41B is a plot showing the specific capacity of Ni3BHT1 as a function of discharge time. [Figure 42] Figure 42 is a plot showing the powder X-ray diffraction patterns of untreated Ni3BHT1 pressed on Ni foam before and after electrochemical cycling according to one embodiment, where the electrochemical cycling was performed at a scan rate of 30 mV / s in a 3-electrode setting, and the cell was held at a voltage of -1.7 V relative to OCP for 5 minutes before being decomposed for analysis. [Figure 43] Figure 43 is a plot showing the 7Li NMR spectrum of immersed and negatively polarized Ni3BHT1 in a 1M LiPF6 / MeCN electrolyte, according to some embodiments. [Figure 44] Figure 44 is a plot showing the 7Li NMR spectrum of immersed and negatively polarized Ni3HITP2 in a 1M LiPF6 / MeCN electrolyte according to some embodiments. [Figure 45] Figure 45 is a plot showing Ni K-edge XANES according to some embodiments. [Figure 46]Figure 46 is a plot showing pre-edge X-ray absorption for untreated Ni3BHT1 and negatively polarized Ni3BHT1 pellets according to some embodiments. [Figure 47] Figure 47 is a plot showing the k3-weighted Fourier transform of EXAFS for untreated and negatively polarized Ni3BHT1 according to some embodiments. [Figure 48] Figure 48 is a plot showing the quality of fitting the k3-weighted Fourier transform of EXAFS for untreated Ni3BHT1 in some embodiments. [Figure 49] Figure 49 is a plot showing the quality of fitting the k3-weighted Fourier transform of EXAFS for untreated Ni3BHT1 in some embodiments. [Figure 50] Figure 50 is a plot showing the C 1s high-resolution X-ray photoelectron spectra of untreated and negatively polarized Ni3BHT1 according to some embodiments. [Figure 51] Figure 51 is a plot showing the Ni 2p high-resolution X-ray photoelectron spectra of untreated and negatively polarized Ni3BHT1 according to some embodiments. [Figure 52] Figure 52 is a plot showing the S 2p high-resolution X-ray photoelectron spectra of untreated and negatively polarized Ni3BHT1 according to some embodiments. [Figure 53] Figure 53 is a plot showing the S 2p high-resolution X-ray photoelectron spectrum of untreated Ni3BHT1 according to some embodiments. [Figure 54] Figure 54 is a plot showing the S 2p high-resolution X-ray photoelectron spectrum of a negatively polarized Ni3BHT1 pellet according to some embodiments. [Figure 55] Figure 55 is a schematic diagram of the intervening ion sorption of Li+ ions between 2D layers of Ni3BHT1 according to one embodiment. [Figure 56] Figure 56 is a schematic diagram of the synthesis of Ni3BHT1 using a BHT ligand according to some embodiments. [Modes for carrying out the invention]

[0013] Detailed explanation Metal-organic structures, supercapacitor electrodes, and supercapacitors are generally provided. Some metal-organic structures described herein may be suitable for use in supercapacitor electrodes, some supercapacitor electrodes described herein may include metal-organic structures described herein, and some supercapacitors described herein may include supercapacitor electrodes described herein.

[0014] In some embodiments, the metal-organic structures described herein have one or more features that enhance their suitability for use in supercapacitor electrodes. For example, a metal-organic structure may have one or more structural features that interact in a preferred manner with one or more types of ions in the supercapacitor electrolyte. For instance, a metal-organic structure may include one or more structural features that allow ions to be readily intercalated and / or absorbed internally, such as pores having a size that allows ions to be readily absorbed internally, and / or spaces between two-dimensional sheets having a size that allows ions to be readily intercalated internally. A metal-organic structure having one or more such features may advantageously exhibit an increased ability to intercalate and / or absorb ions from the electrolyte, resulting in a high degree of neutralization of any charge on its surface by ions from the electrolyte.

[0015] In another embodiment, the metal-organic structure may interact with one or more ions in the supercapacitor electrolyte in a preferred manner during the redox process. For example, the metal-organic structure may contain multiple metal ions configured to undergo a redox reaction, such that ions intercalated and / or absorbed and / or deintercalated and / or desorbed from it balance the charge changes on the internal metal ions. This results in a combination of the metal-organic structure and neutrally charged ions intercalated within it. Such interactions can increase the reversible energy storage capacity of the metal-organic structure by enabling energy storage on the ligands and / or metal ions of the metal-organic structure.

[0016] Some metal-organic structures may possess one or more physical or chemical properties that enhance their performance as supercapacitor electrodes. For example, in some embodiments, the metal-organic structures described herein have advantageously high conductivity. Without adhering to any particular theory, it is conceivable that ligands containing sulfur donor atoms, such as those containing dithiolene groups, may enhance the conductivity of the metal-organic structures in which they are positioned. The p-orbitals of sulfur donor atoms are thought to have favorable energy levels and diffusivity that promote a high degree of overlap with the adjacent d-orbitals of the metal ion to which they coordinate and / or with the pi-orbitals of adjacent portions of the ligand. High conductivity is desirable as it increases the metal-organic structure's ability to transport electrons to and from external circuits, thus reducing its internal resistance.

[0017] As another example, a metal-organic structure may have a chemical composition that allows it to electrochemically interact with one or more ions in the supercapacitor electrolyte as described above. For example, a metal-organic structure may contain multiple metal ions having redox potentials such that a reversible redox reaction can occur during charge-discharge when the charge changes of the metal ions balance out, by intercalation and / or absorption of one or more ions in the supercapacitor electrolyte into and / or deintercalation and / or desorption of one or more ions in the supercapacitor electrolyte from there. The coordination of multiple metal ions in a metal-organic structure with several ligands, such as ligands containing one or more sulfur donor atoms (e.g., ligands containing one or more dithiolene groups), may affect the redox potential of the metal ions and thus promote such behavior.

[0018] In some embodiments, a supercapacitor is provided that includes at least one electrode comprising a metal-organic structure. The metal-organic structure may be one of the metal-organic structures described herein and / or may have one or more of the properties of the metal-organic structures described herein. Such a supercapacitor may preferably exhibit high power delivery capacity and / or energy density for reasons described elsewhere herein with respect to the metal-organic structure.

[0019] In some embodiments, the supercapacitor includes two electrodes, one containing a metal-organic structure and / or the other containing only a metal-organic structure. Such a supercapacitor may include two electrodes, each containing a metal-organic structure, where the metal-organic structure of one electrode differs from the metal-organic structure of the other electrode in one or more ways. For example, the supercapacitor may include a first electrode containing a first metal-organic structure having a first electrode potential, and a second electrode containing a second metal-organic structure having a different electrode potential. The first and second electrode potentials together may provide a desired potential difference across the supercapacitor as a whole. As an example, the two electrodes together may result in a supercapacitor exhibiting a potential difference across them, providing a desired power density and / or capacitance.

[0020] Figure 1 shows one non-limiting embodiment of the metal-organic structure 100. In some embodiments, the metal-organic structure has a two-dimensional structure (e.g., as shown in Figure 2). The metal-organic structure having a two-dimensional structure may be strongly bonded together in two dimensions (e.g., by covalent bonds), or may be weakly bonded together and / or weakly interact with each other in three dimensions (e.g., by van der Waasl interactions). In other words, the interaction energy between multiple two-dimensional sheets may be lower than the bond strength within the multiple two-dimensional sheets. Parts of a two-dimensional structure that are strongly bonded together in two dimensions may form a two-dimensional sheet, which may be extended macroscopically or mesoscopically in two dimensions and may have a thickness in the angstrom or nanometer scale in three dimensions. Such sheets may be aligned with each other or positioned relative to each other by other means. In some embodiments, the two-dimensional structure includes structural motifs that are repeated in two dimensions (e.g., in a two-dimensional sheet) but weakly ordered in three dimensions. As described elsewhere in this specification, the structural motif may be pores, atoms, and / or atomic arrangement configurations. Figure 2 shows one non-limiting embodiment of a metal-organic structure 102 comprising a plurality of two-dimensional sheets 202.

[0021] In some embodiments, the metal-organic structures described herein include a plurality of pores. Such pores may have a variety of suitable forms. Figure 3 shows one non-limiting embodiment of the top surface of a metal-organic structure 104 including a plurality of pores 304. The pores in the metal-organic structures described herein may have some features common to those shown in Figure 3, and / or some features different from those shown in Figure 3. For example, in some embodiments, the metal-organic structure includes a plurality of pores having relatively uniform sizing and / or spacing, such as the pores shown in Figure 3. As also shown in Figure 3, in some embodiments, the plurality of pores may be positioned relative to each other in a manner that forms a repeating lattice throughout the metal-organic structure. As an example of features of a plurality of pores that may differ from those shown in Figure 3, in some embodiments, the plurality of pores occupy a different volume fraction of the metal-organic structure than those shown in Figure 3 (for example, the metal-organic structure may include a plurality of pores that may occupy a much larger volume fraction of the metal-organic structure than those shown in Figure 3). As another example, in some embodiments, the metal-organic structure includes two distinct groups of pores that differ from each other in one or more ways (for example, a first group of pores having a first average pore diameter, and a second group of pores having a second average pore diameter). As a third example, in some embodiments, the metal-organic structure includes a group of pores with non-uniform pore diameters.

[0022] It should be understood that the metal-organic structures described herein may lack porosity when measured by gas adsorption but may contain pores accessible by ions in the electrolyte, and / or may contain surface pores when measured by gas adsorption but not bulk pores when measured by gas adsorption. Similarly, some metal-organic structures described herein may contain bulk pores that are fluid-communicated with the environment outside the metal-organic structure, and some metal-organic structures may contain bulk pores that are not fluid-communicated with the environment outside the metal-organic structure.

[0023] In some embodiments, the metal-organic structure includes a two-dimensional sheet containing pores. Figure 4 shows one non-limiting embodiment of a side view of a two-dimensional sheet in such a metal-organic structure. In Figure 4, the metal-organic structure 206 includes a plurality of pores 306. In Figure 4, the pores pass through the two-dimensional sheet from a first surface to a second opposite surface.

[0024] Some metal-organic structures described herein include a two-dimensional sheet containing pores similar to those shown in Figure 4 in one or more ways, while other metal-organic structures described herein may lack such pores and / or contain other types of pores. For example, in some embodiments, a metal-organic structure contains pores that are lacking in the two-dimensional sheet and / or contains pores in parts of its other than the two-dimensional sheet. As another example, in some embodiments, a metal-organic structure contains pores that do not pass through the overall thickness of the metal-organic structure and / or the thickness of one or more structural features within the metal-organic structure. As yet another example, a metal-organic structure may contain further pores between its internal grains (e.g., grains randomly oriented relative to one another). Such pores may have a wide range of sizes.

[0025] The two-dimensional sheets and / or pores within the metal-organic structures described herein may have a configuration that enhances the usefulness of the metal-organic structure when used as electrodes in a supercapacitor. For example, the two-dimensional sheets may be spaced apart from one another in a manner that allows ions to intercalate between them, and / or the pores within the metal-organic structure may have an average pore diameter that allows ions to be absorbed into them. In some embodiments, the metal-organic structure includes both two-dimensional sheets and pores (and / or includes both two-dimensional sheets that allow ion intercalation between them and pores that allow ions to be absorbed into them).

[0026] Figure 5 shows one non-limiting embodiment of a method for intercalating ions into a metal-organic structure between two two-dimensional sheets. In Figure 5, a plurality of ions 408 are intercalated between two two-dimensional sheets 208 within a plurality of two-dimensional sheets. Figure 6 shows a similar process for absorbing ions into the interior of a metal-organic structure into a plurality of pores located inside. In Figure 6, a plurality of ions 410 are absorbed into a plurality of pores 310. As shown in Figures 5 and 6, the diameter of the ions may be as large as the distance between the two-dimensional sheets and / or the average pore diameter of the pores, which is thought to facilitate the intercalation and / or absorption of ions into their interior. However, it should be understood that some of the metal-organic structures described herein may contain pores with an average pore diameter suitable for intercalating one or more ions each.

[0027] The intercalation and / or absorption of ions into a metal-organic structure may be accompanied by a redox reaction. For example, in some embodiments, the metal-organic structure undergoes a redox reaction, and at least some of the ions intercalated and / or absorbed into the metal-organic structure compensate for the change in charge of the metal-organic structure associated with the redox reaction. As another example, in some embodiments, the metal-organic structure undergoes a redox reaction, and at least some of the ions deintercalated and / or desorbed from the metal-organic structure compensate for the change in charge of the metal-organic structure associated with the redox reaction. The portion of the metal-organic structure undergoing the redox reaction may be the metal ions within it (or any other suitable portion of the metal-organic structure). For example, at least some of the ions may be intercalated and / or absorbed while some of the metal ions within the metal-organic structure are reduced. Similarly, in some embodiments, at least some of the ions may be intercalated and / or absorbed into the metal-organic structure while some of the metal ions within the metal-organic structure are oxidized. Some metal-organic structures may be configured to exhibit this behavior (i.e., they may be configured to interact with multiple ions in such a way that the aforementioned behavior occurs).

[0028] It should also be understood that some of the metal-organic structures described herein may be configured to intercalate, absorb, deintercalate, and / or desorb ions without undergoing redox reactions.

[0029] Redox reactions involving the intercalation and / or absorption of ions into and from metal-organic structures can be facilitated by the presence of metal ions within the metal-organic structure that have a redox potential within a range suitable for undergoing redox reactions during charging and discharging. The redox potential of metal ions within a metal-organic structure may be influenced by one or more of the following factors: the type of metal, the oxidation state of the metal, the type of ligand coordinating to it, the oxidation state of the ligand coordinating to it, the dielectric constant of the electrolyte in the supercapacitor, the charge of the ions in the electrolyte in the supercapacitor, and the polarizability of the ions in the electrolyte in the supercapacitor.

[0030] As described elsewhere in this specification, some embodiments relate to supercapacitor electrodes comprising a metal-organic structure and / or supercapacitors comprising such electrodes. Figure 7 shows one non-limiting embodiment of a supercapacitor electrode 512 comprising a metal-organic structure 112. As shown in Figure 7, some supercapacitor electrodes may include an electron collector (shown as electron collector 612 in Figure 7). Other supercapacitors may lack an electron collector and / or include one or more further components not shown in Figure 7. Figure 8 shows one non-limiting embodiment of a supercapacitor comprising an electrode comprising a metal-organic structure. In Figure 8, the supercapacitor 714 includes a first electrode 514 comprising a metal-organic structure, a second electrode 515, and an electrolyte 814. It should be understood that the supercapacitors described herein may further include other components not shown in Figure 8 (e.g., separators, housings, external circuits, etc.).

[0031] Some of the supercapacitors described herein may be pseudocapacitors. Such a capacitor may include two electrodes, each undergoing Faraday charge transfer during charging and discharging. The Faraday charge transfer may include an intercalation or deintercalation process (and / or absorption or desorption process) after discharge and the other of an intercalation and deintercalation process (and / or absorption or desorption process) after charging. In other words, a pseudocapacitor may include one electrode from which ions are deintercalated (and / or desorbed) after discharge and from which ions are intercalated (and / or absorbed) after charging, and another electrode from which ions are intercalated (and / or absorbed) after discharge and from which ions are deintercalated (and / or desorbed) after charging. Either or both of such processes may further include redox reactions within the electrodes. Such processes may include the dissolution of an electric double layer during discharge and / or the formation of an electric double layer during charging. In some pseudocapacitors, one or both electrodes may include a metal-organic structure as described herein. Ions may be intercalated into and / or deintercalated from the metal-organic structure (and / or absorbed thereand / or desorbed therefrom).

[0032] Some of the supercapacitors described herein may be hybrid capacitors. Such a capacitor may include one electrode that undergoes a Faraday process (e.g., intercalation or deintercalation process, absorption or desorption process, redox reaction) after charging and discharging. This electrode may exhibit the double-layer capacitance already described with respect to pseudocapacitors. The other electrodes may not undergo a Faraday process during charging and discharging (e.g., they may only exhibit double-layer capacitance). In such a supercapacitor, the electrode undergoing the Faraday process may include a metal-organic structure, while the other electrodes may include materials other than metal-organic structures.

[0033] As described above, in some embodiments, the charge-discharge process includes intercalating multiple ions within a metal-organic structure. This may occur during the use of a supercapacitor containing a metal-organic structure for power delivery, and / or as a prior conditioning process. For example, some embodiments may include a conditioning process in which multiple ions are intercalated within a metal-organic structure to facilitate the intercalation of further ions (e.g., different types of ions) into its interior during a further process. As an example, the process may include intercalating multiple relatively large ions within a metal-organic structure in a manner such as increasing the spacing between two-dimensional sheets inside. Such ions may then be deintercalated from the metal-organic structure, after which the metal-organic structure may permanently expand. Subsequent processes may include intercalating further ions into the metal-organic structure (for example, ions having a size greater than the spacing between two-dimensional sheets before the intercalation of the first plurality of ions into it, and having a size smaller than the spacing between two-dimensional sheets after the deintercalation of the first plurality of ions from it).

[0034] In some embodiments, several relatively large ions have opposite charges to several ions that are subsequently intercalated into the metal-organic structure. A process for conditioning the metal-organic structure in the presence of these ions may include first charging the metal-organic structure to a first charge (e.g., positive), and then charging the metal-organic structure to a second opposite charge (e.g., negative). When the metal-organic structure is charged to a second opposite charge, several relatively large ions may be deintercalated from it, and the second group of ions may be intercalated into it.

[0035] The metal-organic structures described herein may include multiple metal ions coordinated by multiple ligands. The term “metal-organic structure” is given its common meaning in the art and refers to a one-, two-, or three-dimensional coordination polymer containing metal ions and ligands that function as organic structural units, some of which are chemically bonded to at least one ligand (e.g., two-, three-, and / or polydentate ligands). In addition to being coordinated to at least one organic structural unit, the metal ions may also be coordinated to one or more auxiliary ligands, as described in more detail herein.

[0036] The metal-organic structures described herein may have a variety of suitable geometric shapes. In some embodiments, the metal-organic structure comprises multiple metal ions, at least some of which are coordinated to one or more ligands. For example, in some embodiments, the metal-organic structure comprises multiple metal ions, at least some of which are associated to two, three, or four ligands. The metal-organic structure may further contain multiple ligands, at least some of which are coordinated to one or more metal ions. For example, at least some of the ligands in the metal-organic structure (e.g., at least some of the metal-organic structure and / or each non-auxiliary ligand) may be coordinated to two or more metal ions. In some embodiments, the metal-organic structure comprises multiple ligands, at least some of which are coordinated to three or four metal ions. The following are further non-limiting embodiments of the metal ions and ligands in the metal-organic structures described herein that may have: at least a portion of metal ions coordinated with at least two ligands, at least a portion of ligands coordinated to two metal ions, at least a portion of metal ions coordinated with three ligands, at least a portion of ligands coordinated to three metal ions, at least a portion of metal ions coordinated with two ligands, and each ligand coordinated to three metal ions.

[0037] The charges of metal ions and ligands suitable for use in the metal-organic structures described herein can generally be selected as desired. For example, a metal-organic structure may contain ligands having charges of (-1), (-2), (-3), (-4), (-5), and / or (-6). In another example, a metal-organic structure may contain metal ions having charges of (+1), (+2), and / or (+3). In uncharged metal-organic structures, the charge of each ligand is typically balanced by the charge of the coordinated metal ion, thereby allowing any ion to be absorbed and / or intercalated within the metal-organic structure.

[0038] It should be understood that the metal-organic structures described herein may contain two or more types of ligands and / or two or more types of ions. Where two or more types of ligands are provided, the relative amounts of each type of ligand can be selected as desired. Similarly, where two or more types of metal ions are provided, the relative amounts of each type of metal ion can be selected as desired. It should also be understood that some metal-organic structures described herein may contain a single type of ligand and / or a single type of metal ion.

[0039] Ligands containing various suitable functional groups that coordinate to metal ions may be used in the metal-organic structures described herein. Some metal-organic structures may contain polydentate (e.g., bidentate) ligands. Such ligands may coordinate to two or more metal ions, and may coordinate to each metal ion in a polydentate manner. For example, a ligand coordinating to two metal ions may each be bidentate and contain two sets of two functional groups, each set of two functional groups coordinating to a metal ion. As another example, a ligand coordinating to three metal ions may each be bidentate and contain three sets of two functional groups, each set of two functional groups coordinating to a metal ion. As a third example, a ligand coordinating to four metal ions may each be bidentate and contain four sets of two functional groups, each set of two functional groups coordinating to a metal ion.

[0040] The functional groups that coordinate to a metal ion in a polydentate manner may take various appropriate forms. In some embodiments, polydentate coordination is achieved via vicinal functional groups (e.g., ortho functional groups). In other words, when the ligand is polydentate, the combination of functional groups configured to coordinate to a single metal ion may be adjacent (e.g., ortho). In some embodiments, polydentate coordination is achieved via functional groups other than adjacent functional groups (e.g., ortho functional groups, para functional groups). As mentioned above, this means that the combination of functional groups configured to coordinate to a single metal ion may be other than vicinal (e.g., meta, para).

[0041] In some embodiments, the ligand coordinates to a single metal ion by a single type of functional group. For example, the ligand may coordinate to a single metal ion by two or more identical functional groups. In some such embodiments, all of the metal ion coordinated by the ligand is coordinated by a single type of functional group within it.

[0042] In other embodiments, the ligands coordinate to a single metal ion by two or more types of functional groups. For example, the metal ion may be coordinated by a plurality of ligands having ortho functional groups, or by a plurality of ligands having para and / or meta functional groups. In some embodiments, a first plurality of ligands containing ortho functional groups may coordinate to a plurality of metal ions via the ortho functional groups to form a two-dimensional sheet, and a second plurality of ligands containing para and / or meta functional groups may coordinate to a plurality of metal ions via the para and / or meta functional groups to form pillars that join the two-dimensional sheet together.

[0043] It should also be understood that some embodiments may relate to metal-organic structures in which multiple ligands include ligands containing two or more types of functional groups, and / or multiple metal ions include metal ions coordinated by two or more types of functional groups.

[0044] Some metal-organic structures described herein can coordinate to metal ions via particularly advantageous functional groups. For example, in some embodiments, the metal-organic structure coordinates to the metal ion via a functional group containing a sulfur donor atom (e.g., a vicinal thiolate functional group, an ortho thiolate functional group, or a thiolene functional group). As another example, in some embodiments, the metal-organic structure coordinates to the metal ion via an imine functional group (e.g., a vicinal hymine functional group, or an ortho imine functional group).

[0045] The organic cores of the ligands described herein may have a variety of suitable structures. In some embodiments, the metal-organic structure includes a ligand having a conductive organic core. Such an organic core may include a conjugated double bond and / or an aromatic moiety. For example, in some embodiments, the metal-organic structure includes a ligand containing a condensed aryl and / or heteroaryl ring. Such a ligand may have an organic core having a rigid structure formed from the condensed aryl and / or heteroaryl ring. Non-limiting examples of suitable aryl and heteroaryl rings include benzyl, thiophenyl, carbazolyl, pyrrolyl, indolyl, and furanyl rings.

[0046] One example of a proper ligand structure is: [ka] In the formula, n is 1, 2, or 3, C represents one or more bonds formed between ring A and each ring B, and R is a functional group coordinated to a metal ion. In some embodiments, each R is -S. In some embodiments, each R is -NH. In some cases, n is 1. In some cases, n is 2. In some cases, n is 3.

[0047] Other examples of appropriate structures with respect to ligands include: [ka] It includes, and in the formula, each R 1R' is the same or different and selected from the group consisting of hydrogen, -NO2, -R', -F, -Cl, -Br, -I, -CN, -NC, -SO3R', -SO3H, -OR', -OH, -SR', -SH, -PO3R', -PO3H, -CF3, -NR'2, -NHR', and -NH2; each R' is the same or different and optionally substituted alkyl or optionally substituted aryl; each R is a functional group that coordinates to a metal ion. In some embodiments, both the R group and at least some (or all) of the R' groups are functional groups that coordinate to a metal ion. In some embodiments, each R is -S. In some embodiments, each R is -NH. In some embodiments, each R 1 R' is hydrogen. In some embodiments, each R' is H.

[0048] Further examples of appropriate ligand structures include: [ka] [ka] It includes, and in the formula, each R 1 X is the same or different and selected from the group consisting of hydrogen, -NO2, -R', -F, -Cl, -Br, -I, -CN, -NC, -SO3R', -SO3H, -OR', -OH, -SR', -SH, -PO3R', -PO3H, -CF3, -NR'2, -NHR', and -NH2; each X is the same or different and selected from the group consisting of NR', O, S, Se, and Te; each R' is the same or different and optionally substituted alkyl or optionally substituted aryl; each R is a functional group that coordinates to a metal ion. In some embodiments, each R is -S. In some embodiments, each R is -NH. In some embodiments, both the R group and at least some (or all) of the R' groups are functional groups that coordinate to a metal ion. In some embodiments, each R 1is hydrogen. In some embodiments, each X is the same or different and is selected from the group consisting of NR’, O, and S. In some embodiments, each X is NR’. In some embodiments, each X is O. In some embodiments, each X is S. In some embodiments, each X is Se. In some embodiments, each X is Te. In some embodiments, each R’ is H.

[0049] As described elsewhere herein, the metal ions included in the metal organic structures described herein may be monovalent, divalent, and / or trivalent. Such metal ions may be transition metal ions, noble metal ions, and / or post-transition metal ions. In some embodiments, each metal ion is a monovalent metal ion. Non-limiting examples of monovalent metal ions are Ag + , Cu + , and Au + . In certain cases, the metal organic structure includes Cu + (e.g., as the only type of metal ion, as one of two or more types of metal ions). In some embodiments, each metal ion is a divalent metal ion. Non-limiting examples of divalent metal ions are Mg 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Pd 2+ , Pt 2+ , Ru 2+ , Cd 2+ , Zn 2+ , Pb 2+ , Hg 2+ , V 2+ , Cr 2+ , and Ni 2+ . In certain cases, the metal ion is Ni 2+ (e.g., as the only type of metal ion, as one of two or more types of metal ions). In certain cases, the metal ion is Cu 2+(For example, as a single type of metal ion, or as one of two or more types of metal ions). In some embodiments, each ion is a trivalent metal ion. A non-limiting example of a trivalent metal ion is Fe 3+ , V 3+ Ti 3+ , Sc 3+ , Al 3+ In 3+ , Ga 3+ Mn 3+ Co 3+ , and Cr 3+ In some embodiments, the metal-organic structure includes nickel ions, cobalt ions, iron ions, copper ions, platinum ions, and / or palladium ions (e.g., in monovalent, divalent, and / or trivalent forms).

[0050] As described elsewhere in this specification, some metal-organic structures contain metal ions with redox potentials suitable for oxidation reactions during charging and discharging (e.g., in supercapacitors). For example, metal-organic structures have redox potentials greater than or equal to -3V, greater than or equal to -2.75V, greater than or equal to -2.5V, greater than or equal to -2.25V, greater than or equal to -2V, greater than or equal to -1.75V, greater than or equal to -1.5V, greater than or equal to -1.25V, greater than or equal to -1V, greater than or equal to -0.75V, greater than or equal to -0.5V, greater than or equal to -0.25V It may also contain multiple ions having redox potentials greater than or equal to 0V, greater than or equal to 0.25V, greater than or equal to 0.5V, greater than or equal to 0.75V, greater than or equal to 1V, greater than or equal to 1.25V, greater than or equal to 1.5V, greater than or equal to 1.75V, greater than or equal to 2V, greater than or equal to 2.25V, greater than or equal to 2.5V, or greater than or equal to 2.75V.In some embodiments, the metal-organic structure is less than or equal to 3V, less than or equal to 2.75V, less than or equal to 2.5V, less than or equal to 2.25V, less than or equal to 2V, less than or equal to 1.75V, less than or equal to 1.5V, less than or equal to 1.25V, less than or equal to 1V, less than or equal to 0.75V, less than or equal to 0.5V, less than or equal to 0.25V, less than or equal to 0V This includes multiple ions having redox potentials of full or equal to -0.25V, less than or equal to -0.5V, less than or equal to -0.75V, less than or equal to -1V, less than or equal to -1.25V, less than or equal to -1.5V, less than or equal to -1.75V, less than or equal to -2V, less than or equal to -2.25V, less than or equal to -2.5V, or less than or equal to -2.75V. Combinations of the ranges mentioned above are also possible (e.g., greater than or equal to -3V and less than or equal to 3V, greater than or equal to -3V and less than or equal to 2V). Other ranges are also possible.

[0051] The redox potential of metal ions in a metal-organic structure may be determined by cyclic voltammetry to determine the redox potential of the metal-organic structure, and by X-ray adsorption spectroscopy to confirm that the redox potential is that of a metal ion.

[0052] In some embodiments, more than one type of metal ion may be used, for example, a first type of metal ion and a second type of metal ion. The difference between the types of metal ions may relate to the element forming the metal ion and / or the valency of the metal ion. For example, some metal-organic structures may contain two or more types of metal ions with various valencies. Such types of metal ions may be the same type of metal but in different redox states (e.g., Cu + and Cu 2+) may also contain different types of metals in different redox states (e.g., Cu + and Ni 2+ ) may also contain. As another example, two different types of metal ions may be different types of metals in the same redox state (e.g., Cu 2+ and Ni 2+ ) may contain. It should also be understood that some metal-organic structures may contain only metal ions with a single valency and / or only one type of metal.

[0053] If a metal-organic structure may contain two or more types of metal ions with different valencies, the combination of metal ion types and the relative amounts of each type of metal ion can generally be chosen as desired. In some embodiments, the metal-organic structure contains one or more monovalent metal ions and one or more divalent metal ions. In some such embodiments, the metal-organic structure may contain one or more ligands that are redox-active and / or can adapt to various redox states of the metal ions.

[0054] In some embodiments, the metal-organic structure includes multiple auxiliary ligands. In such cases, at least some of the multiple metal ions within it may associate with one or more auxiliary ligands. The auxiliary ligands may be positioned above and / or below the metal ions to which they associate (e.g., as apical ligands). Some suitable auxiliary ligands may be charged, while others may not. Non-limiting examples of auxiliary ligands include halides (e.g., chlorine, fluorine, bromine, iodine), salts (e.g., nitrates, carbonates, sulfons, etc.), and coordinating solvents (e.g., water, pyridine, tetrahydrofuran, diethyl ether, etc.).

[0055] Two examples of metal-organic structures that are considered particularly suitable for use in supercapacitor electrodes are shown below: [ka] In the formula, M is a metal ion. For example, M may be a transition metal ion such as an iron ion, a cobalt ion, a nickel ion, and / or a copper ion.

[0056] In some embodiments, the metal-organic structures described herein contain little to no excess metal ions. That is, the metal-organic structures may essentially not contain metal ions that are not ligand-coordinated (and / or ligands that are not coordinated by functional groups configured to coordinate to metal ions). Such uncoordinated metal ions are also referred to as “free metal ions” elsewhere in this specification. In some embodiments, the metal-organic structures contain free metal ions in amounts less than or equal to 0.5% by weight, less than or equal to 0.4% by weight, less than or equal to 0.3% by weight, less than or equal to 0.2% by weight, less than or equal to 0.1% by weight, less than or equal to 0.05% by weight, less than or equal to 0.03% by weight, less than or equal to 0.02% by weight, less than or equal to 0.01% by weight, less than or equal to 0.005% by weight, or less than or equal to 0.001% by weight.

[0057] The weight percentage of free metal ions within the metal-organic structure may be determined by X-ray photoelectron spectroscopy.

[0058] In some embodiments, the supercapacitor includes two electrodes, each containing one of the metal-organic structures described above (for example, the cathode contains one of the metal-organic structures described above, and the anode contains another of the metal-organic structures described above). One electrode may contain a metal-organic structure in which a ligand containing a sulfur donor atom is coordinated to a metal ion by a sulfur donor atom, and the other electrode may contain a metal-organic structure in which a ligand containing an imine functional group is coordinated to a metal ion by an imine functional group.

[0059] As described above, in some embodiments, the metal-organic structures described herein have one or more physical properties that enhance their suitability for use in supercapacitor electrodes.

[0060] For example, a metal-organic structure may contain multiple pores. These multiple pores may have an advantageous average pore diameter. For instance, the multiple pores may have an average pore diameter of 0.3 nm or more, 0.5 nm or more, 0.75 nm or more, 1 nm or more, 1.25 nm or more, 1.5 nm or more, 1.75 nm or more, 2 nm or more, 2.25 nm or more, 2.5 nm or more, or 2.75 nm or more. In some embodiments, multiple pores have an average pore diameter of less than or equal to 3 nm, less than or equal to 2.75 nm, less than or equal to 2.5 nm, less than or equal to 2.25 nm, less than or equal to 2 nm, less than or equal to 1.75 nm, less than or equal to 1.5 nm, less than or equal to 1.25 nm, less than or equal to 1 nm, less than or equal to 0.75 nm, or less than or equal to 0.5 nm. Combinations of the ranges mentioned above are also possible (e.g., greater than or equal to 0.3 nm and less than or equal to 3 nm). Other ranges are also possible.

[0061] The average pore size of multiple pores positioned using an ordered method is determined by X-ray crystallography (e.g., pores positioned to form a lattice, pores forming a repeating structure on a two-dimensional sheet). The average pore size of multiple pores positioned using an irregular and / or random method may be determined by Brunauer-Emmett-Teller (BET) adsorption measurement.

[0062] When a metal-organic structure contains multiple pores, the multiple pores may include pores having various suitable shapes. For example, a metal-organic structure may include a two-dimensional sheet containing pores of circular, triangular, elliptical, quadrilateral, pentagonal, hexagonal, and / or any other suitable shape. As another example, a metal-organic structure may include three-dimensional pores having spherical, oval, cylindrical, and / or any other suitable shape. In some embodiments, a metal-organic structure may include pores that are close to but not identical to one of the shapes mentioned above. For example, a metal-organic structure may include pores that can depict one of the shapes mentioned above, with at least 80%, at least 90%, at least 95%, at least 97%, or at least 99% of their area overlapping, and / or pores with at least 80%, at least 90%, at least 95%, at least 97%, or at least 99% of their area overlapping one of the shapes mentioned above.

[0063] If the metal-organic structure contains multiple pores, these multiple pores may include pores bounded by various appropriate numbers of metal ions. For example, in some embodiments, the multiple pores include pores bounded by more than or equal to 3 metal ions, more than or equal to 4 metal ions, or more than or equal to 5 metal ions. In some embodiments, the multiple pores include pores bounded by less than or equal to 6 metal ions, less than or equal to 5 metal ions, or less than or equal to 4 metal ions. Combinations of the ranges mentioned above are also possible (e.g., greater than or equal to 3 and less than or equal to 6). Other ranges are also possible.

[0064] When a metal-organic structure contains multiple pores, these multiple pores may include pores whose boundaries are formed by various appropriate numbers of donor atoms (e.g., sulfur atoms). For example, in some embodiments, the multiple pores include pores whose boundaries are formed by more than or equal to three donor atoms, more than or equal to four donor atoms, more than or equal to five donor atoms, more than or equal to six donor atoms, more than or equal to seven donor atoms, more than or equal to eight donor atoms, more than or equal to nine donor atoms, more than or equal to ten donor atoms, or more than or equal to eleven donor atoms. In some embodiments, the pores include pores whose boundaries are formed by fewer than or equal to 12 donor atoms, fewer than or equal to 10 donor atoms, fewer than or equal to 9 donor atoms, fewer than or equal to 8 donor atoms, fewer than or equal to 7 donor atoms, fewer than or equal to 6 donor atoms, fewer than or equal to 5 donor atoms, or fewer than or equal to 4 donor atoms. Combinations of the ranges mentioned above are also possible (e.g., more than or equal to 3 and less than or equal to 12). Other ranges are also possible.

[0065] As another example of properties that may enhance their suitability for use in supercapacitor electrodes, the metal-organic structure may include two-dimensional sheets having one or more desired structural features. For example, the metal-organic structure may include two-dimensional sheets having a desired average spacing. In some embodiments, the metal-organic structure includes two-dimensional sheets spaced apart from each other with average spacings of greater than or equal to 0.3 nm, greater than or equal to 0.4 nm, greater than or equal to 0.5 nm, greater than or equal to 0.6 nm, greater than or equal to 0.7 nm, greater than or equal to 0.8 nm, or greater than or equal to 0.9 nm. In some embodiments, the metal-organic structure includes two-dimensional sheets spaced apart from each other with average spacings of less than or equal to 1 nm, less than or equal to 0.9 nm, less than or equal to 0.8 nm, less than or equal to 0.7 nm, less than or equal to 0.6 nm, less than or equal to 0.5 nm, or less than or equal to 0.4 nm. Combinations of the ranges mentioned above are also possible (for example, greater than or equal to 0.3 nm and less than or equal to 1 nm). Other ranges are also possible.

[0066] The average spacing between two-dimensional sheets may be determined by X-ray crystallography.

[0067] When a metal-organic structure includes two-dimensional sheets, they may be positioned relative to each other in various appropriate ways. For example, some metal-organic structures may include two-dimensional sheets positioned relative to each other in an overlapping manner. Such a metal-organic structure may include two-dimensional sheets having an AA-type lamination. In some embodiments, the metal-organic structure includes two-dimensional sheets positioned relative to each other in an alternating manner. Such a metal-organic structure may include two-dimensional sheets having an AB-type lamination and / or two-dimensional sheets that are maximally offset relative to each other (e.g., half the repetition distance of the motifs inside). Other positioning of the two-dimensional sheets is also possible. For example, the metal-organic structure may include two-dimensional sheets positioned relative to each other in an overlapping and alternating manner, and / or two-dimensional sheets having an ABC-type or other type of lamination.

[0068] As a third example of properties that can enhance their suitability for use in supercapacity electrodes, metal-organic structures may have redox potentials that facilitate redox reactions during charging and discharging. For example, a metal-organic structure may have redox potentials greater than or equal to -3V, greater than or equal to -2.7V, greater than or equal to -2.5V, greater than or equal to -2.3V, greater than or equal to -2V, greater than or equal to -1.7V, greater than or equal to -1.5V, greater than or equal to -1.3V, greater than or equal to -1V, greater than or equal to -0.7V, greater than or equal to -0.5V, greater than or equal to -0.3V, and It may have a redox potential equal to, greater than or equal to 0V, greater than or equal to 0.2V, greater than or equal to 0.5V, greater than or equal to 0.7V, greater than or equal to 1V, greater than or equal to 1.3V, greater than or equal to 1.5V, greater than or equal to 1.7V, greater than or equal to 2V, greater than or equal to 2.3V, greater than or equal to 2.5V, or greater than or equal to 2.7V.In some embodiments, the metal-organic structure has a redox potential of less than or equal to 3V, less than or equal to 2.7V, less than or equal to 2.5V, less than or equal to 2.3V, less than or equal to 2V, less than or equal to 1.7V, less than or equal to 1.5V, less than or equal to 1.3V, less than or equal to 1V, less than or equal to 0.7V, less than or equal to 0.5V, less than or equal to 0.2V, less than or equal to 0V, less than or equal to -0.3V, less than or equal to -0.5V, less than or equal to -0.7V, less than or equal to -1V, less than or equal to -1.3V, less than or equal to -1.5V, less than or equal to -1.7V, less than or equal to -2V, less than or equal to -2.3V, less than or equal to -2.5V, or less or equal to -2.7V relative to a standard hydrogen electrode. Combinations of the ranges mentioned above are also possible (for example, greater than or equal to -3V and less than or equal to -3V, greater than or equal to -2.7V and less than or equal to -1.3V, greater than or equal to -2.7V and less than or equal to -0.2V, or greater than or equal to -2V and less than or equal to -1.3V). Other ranges are also possible. In some embodiments, the supercapacitor may include two metal-organic structures, each having a redox potential in one or more of the ranges listed above (for example, one metal-organic structure having a redox potential greater than or equal to -2.7V and less than or equal to -0.2V, and the other metal-organic structure having a redox potential greater than or equal to -2V and less than or equal to -1.3V).

[0069] The redox potential of a metal-organic structure may be determined by cyclic voltammetry.

[0070] As a fourth example of properties that may enhance their suitability for use in supercapacitor electrodes, metal-organic structures may have advantageously high conductivity. In some embodiments, the metal-organic structures described herein have conductivity greater than or equal to 1 S / cm, greater than or equal to 2 S / cm, greater than or equal to 5 S / cm, greater than or equal to 7 S / cm, greater than or equal to 10 S / cm, greater than or equal to 15 S / cm, greater than or equal to 20 S / cm, greater than or equal to 25 S / cm, greater than or equal to 30 S / cm, greater than or equal to 35 S / cm, greater than or equal to 40 S / cm, and greater than or equal to 50 S / cm. It has an conductivity greater than or equal to 60 S / cm, greater than or equal to 70 S / cm, greater than or equal to 80 S / cm, greater than or equal to 90 S / cm, greater than or equal to 100 S / cm, greater than or equal to 150 S / cm, greater than or equal to 200 S / cm, greater than or equal to 500 S / cm, greater than or equal to 750 S / cm, greater than or equal to 1000 S / cm, or greater than or equal to 1500 S / cm.The metal-organic structure may have an conductivity of less than or equal to 2000 S / cm, less than or equal to 1500 S / cm, less than or equal to 1000 S / cm, less than or equal to 750 S / cm, less than or equal to 500 S / cm, less than or equal to 200 S / cm, less than or equal to 150 S / cm, less than or equal to 100 S / cm, less than or equal to 90 S / cm, less than or equal to 80 S / cm, less than or equal to 70 S / cm, less than or equal to 60 S / cm, less than or equal to 50 S / cm, less than or equal to 40 S / cm, less than or equal to 35 S / cm, less than or equal to 30 S / cm, less than or equal to 25 S / cm, less than or equal to 20 S / cm, less than or equal to 15 S / cm, less than or equal to 10 S / cm, less than or equal to 7 S / cm, less than or equal to 5 S / cm, or less than or equal to 2 S / cm. Combinations of the ranges mentioned above are also possible (for example, greater than or equal to 1 S / cm and less than or equal to 2000 S / cm, or greater than or equal to 1 S / cm and less than or equal to 100 S / cm). Other ranges are also possible.

[0071] The conductivity of a metal-organic structure may be determined by performing a two-probe DC measurement at 25°C on a 500 nm thick film of the metal-organic structure.

[0072] As a fifth example of properties that may enhance their suitability for use in supercapacitor electrodes, metal-organic structures may have advantageously high charge mobility. The charge mobility of metal-organic structures is 0.1 cm². 2 Greater than or equal to (V·s), 0.5cm 2 / (V·s) is greater than or equal to 1cm 2 / (V·s) is greater than or equal to 2cm 2 / (V·s) is greater than or equal to 3cm 2 / (V·s) is greater than or equal to 4cm 2 / (V·s) greater than or equal to 5cm 2 Greater than or equal to (V·s), 7.5cm 2 / (V·s) greater than or equal to 10cm 2 / (V·s) greater than or equal to 20cm 2 / (V·s) greater than or equal to 30cm 2 / (V·s) greater than or equal to 40cm 2 / (V·s) greater than or equal to 50cm 2 / (V·s) greater than or equal to 75cm 2 Greater than or equal to (V·s), 100cm 2 Greater than or equal to (V·s), 250cm 2 / (V·s) is greater than or equal to 500cm 2 Greater than or equal to (V·s), or 750cm 2 / (V·s) may be greater than or equal to it. In some embodiments, the metal-organic structure is 1000 cm 2 / (V·s) less than or equal to 750cm 2 / (V·s) less than or equal to 500cm 2 / (V·s) less than or equal to 250cm 2 / (V·s) less than or equal to 100cm 2 / (V·s) less than or equal to 75cm 2 / (V·s) less than or equal to 50cm 2 / (V·s) less than or equal to 40cm 2 / (V·s) less than or equal to 30cm 2 / (V·s) less than or equal to 20cm 2 / (V·s) less than or equal to 10cm 2 / (V·s) less than or equal to 7.5cm 2 / (V·s) less than or equal to 5cm 2 / (V·s) less than or equal to 4cm 2 / (V·s) less than or equal to 3cm 2 / (V·s) less than or equal to 2cm 2 / (V·s) less than or equal to 1cm 2 Less than or equal to (V·s), or 0.5 cm 2 The charge mobility is less than or equal to / (V·s). Combinations of the ranges mentioned above are also possible (e.g., 0.1 - 0.5 cm). 2 / (V·s) greater than or equal to and 1000 0.5cm 2 (Less than or equal to (V·s)). Other ranges are also possible.

[0073] The charge mobility of a metal-organic structure may be determined by performing Hall measurements on a single crystal of the metal-organic structure.

[0074] The metal-organic structures described herein may be synthesized by a variety of suitable methods. In some cases, a method for synthesizing a metal-organic structure involves exposing a plurality of metal ions to a plurality of precursor ligands in the presence of an oxidizing agent and a base in order to form a metal-organic structure comprising a plurality of metal ions, each of which is coordinated to at least a plurality of ligands. In some embodiments, the metal ions are provided as cations of a salt, and at least one of the provided precursor ligands comprises a functional group configured to react with the cation (e.g., a thiol functional group, an imine functional group). The functional group may be polydentate (e.g., bidentate) as described above. During the reaction, the functional group of the precursor ligand configured to react with the cation is oxidized to the corresponding functional group and coordinates to the metal ion in the final metal-organic structure (e.g., the final functional group comprising a sulfur donor atom and / or an imine functional group). For example, with respect to a precursor ligand containing an ortho-phenylenediamine group, during the reaction process, the precursor ligand is oxidized so that each ortho-phenylenediamine group is converted into an ortho-phenylenediamine group, which then coordinates to the metal ion.

[0075] The metal ions and precursor ligands may be supplied in any suitable amount. In some embodiments, the molar ratio of the metal ions to the precursor ligands may be based on the coordination of the metal ions to the ligands. For example, in an embodiment where the ligands coordinate to three metal ions and each metal ion associates with two ligands, the molar ratio of the metal ions to the precursor ligands may be about 3:2. In another example in the embodiment, where the ligands coordinate to two metal ions and each metal ion associates with one ligand, the molar ratio of the metal ions to the precursor ligands may be about 2:1. In some embodiments, the precursor ligands are supplied in a molar excess compared to the metal ions.

[0076] As mentioned above, metal ions may be provided in the form of salts. Non-limiting examples of anions that may be contained in salts include chlorides, fluorides, bromides, iodides, triflates, and BF4. - PF6 - NO3 - SO4 2- , and ClO4 - It contains salt. In some cases, the salt is SO4 2- Contains anions.

[0077] One example of a suitable structure for a precursor ligand is: [ka] In the formula, n is 1, 2, or 3, C represents one or more bonds formed between ring A and each ring B, and R is a functional group configured to coordinate to a metal ion. In some embodiments, each R is -S. In some embodiments, each R is -NH. In some cases, n is 1. In some cases, n is 2. In some cases, n is 3.

[0078] Other examples of appropriate structures for precursor ligands include: [ka] It includes, and in the formula, each R 1 R' is the same or different and selected from the group consisting of hydrogen, -NO2, -R', -F, -Cl, -Br, -I, -CN, -NC, -SO3R', -SO3H, -OR', -OH, -SR', -SH, -PO3R', -PO3H, -CF3, -NR'2, -NHR', and -NH2; where each R' is the same or different and optionally substituted alkyl or optionally substituted aryl; where each R is a functional group configured to coordinate to a metal ion. In some embodiments, both the R group and at least some (or all) of the R' groups are functional groups configured to coordinate to a metal ion after oxidation. In some embodiments, each R is -S. In some embodiments, each R is -NH. In some embodiments, each R 1 R' is hydrogen. In some embodiments, each R' is H.

[0079] Further examples of structures suitable for precursor ligands include: [ka] [ka] It includes, and in the formula, each R 1are the same or different and are selected from the group consisting of hydrogen, -NO2, -R’, -F, -Cl, -Br, -I, -CN, -NC, -SO3R’, -SO3H, -OR’, -OH, -SR’, -SH, -PO3R’, -PO3H, -CF3, -NR’2, -NHR’, and -NH2; wherein each X is the same or different and is selected from the group consisting of NR’, O, S, Se, and Te; wherein each R’ is the same or different and is optionally substituted alkyl or optionally substituted aryl; wherein each R is a functional group configured to coordinate to a metal ion. In some embodiments, each R is -S. In some embodiments, each R is -NH. In some embodiments, both the R group and at least a portion (or all) of the R’ groups are functional groups configured to coordinate to a metal ion after oxidation. In some embodiments, each R 1 is hydrogen. In some embodiments, each X is the same or different and is selected from the group consisting of NR’, O, and S. In some embodiments, each X is NR’. In some embodiments, each X is O. In some embodiments, each X is S. In some embodiments, each X is Se. In some embodiments, each X is Te. In some embodiments, each R’ is H.

[0080] Any suitable base may be utilized in the synthetic methods described herein. Non-limiting examples of bases include NR”3 (wherein each R” is the same or different and is hydrogen, optionally substituted alkyl, or optionally substituted aryl); QOH (wherein Q is a cation (e.g., a metal cation, a metalloid cation, NH4 +); and acetate are included. In some embodiments, the base is NH3 or NH4OH. In some embodiments, the base is selected to have a higher pH compared to the groups on the precursor ligand configured to react with metal ions to coordinate to them. Any suitable oxidizing agent may be used. In some embodiments, the oxidizing agent is oxygen. In some embodiments, the oxidizing agent is a chemical oxidizing agent. Non-limiting examples of oxidizing agents include air, oxygen, ferricinium, nitrosonium, and Ag 2+ Ag + Fe 3+ MnO4 - , and CrO4 - It includes. The oxidizing agent may be present in an amount suitable for assisting the oxidation of the precursor ligand. In some embodiments, the oxidizing agent is present in excess.

[0081] Any suitable solvent may be used in the synthesis methods described herein. Non-limiting examples of solvents include water, methanol, ethanol, propanol, benzene, p-cresol, toluene, xylene, diethyl ether, glycol, diethyl ether, petroleum ether, hexane, cyclohexane, pentane, methylene chloride, chloroform, carbon tetrachloride, dioxane, tetrahydrofuran (THF), dimethyl sulfoxide, dimethylformamide, hexamethyl phosphate triamide, ethyl acetate, pyridine, triethylamine, picoline, and mixtures thereof. In some embodiments, the solvent is water.

[0082] The synthesis methods described herein may be carried out at any suitable temperature. In some cases, the reaction is carried out at approximately room temperature (e.g., 25°C, 20°C, 20°C to 25°C, etc.). However, in other cases, the reaction is carried out at temperatures lower or higher than room temperature. In some embodiments, the reaction is carried out at temperatures of 25°C to 100°C, 35°C to 95°C, 45°C to 85°C, or 55°C to 75°C.

[0083] Metal-organic structures synthesized using the methods described herein may be purified using techniques known to those skilled in the art. In some embodiments, the synthesized metal-organic structures may be washed and, optionally, boiled and / or ultrasonically treated with a Soxhlet extractor (e.g., to remove excess starting material).

[0084] The synthesis methods described herein may be provided for the rapid synthesis of a wide range of metal-organic structures. The ability to rapidly synthesize metal-organic structures may be useful for screening known metal-organic structures as well as new ones to determine their suitability for use in supercapacitor electrodes.

[0085] The metal-organic structures described herein may, in some cases, be formed as a film on the surface of a material. The film may be formed using techniques known to those skilled in the art. For example, the film may be formed by spin casting, drop casting, dip coating, roll coating, screen coating, spray coating, screen printing, inkjet, etc. In some cases, the thickness of the film may be less than or equal to 100 microns, less than or equal to 10 microns, less than or equal to 1 micron, less than or equal to 100 nm, less than or equal to 10 nm, or less than or equal to 1 nm. In some cases, the film may have a thickness greater than or equal to 1 mm. Other ranges are also possible. The thickness of the film may be measured by microscopy.

[0086] As described above, the supercapacitors described herein may contain an electrolyte, the electrodes described herein may be suitable for use with the electrolyte, and / or metal-organic structures may be configured to interact with the electrolyte. The electrolyte is typically configured to facilitate ion intercalation and / or absorption to one or more of the supercapacitor electrodes, and / or to facilitate the formation and / or dissolution of an electrical double layer, in order to facilitate ion transfer between the supercapacitor electrodes. However, the electrolyte is typically configured to prevent obvious electron transfer between them. In other words, the electrolyte is typically ionically conductive but not electrically conductive. Without adhering to any particular theory, liquid electrolytes may be considered particularly suitable for use inside and / or with the supercapacitors, electrodes, and / or metal-organic structures described herein, because they can have particularly high ion mobility. In some embodiments, gel electrolytes, solid electrolytes (e.g., polymer electrolytes), and / or liquid electrolytes in salts may also be suitable or alternative.

[0087] In some embodiments, the electrolytes described herein include a solvent. The solvent may be solvated with ions from the salt dissolved therein. For example, the electrolyte may contain water (i.e., it may be an aqueous electrolyte). In other embodiments, the electrolyte may be deficient in water (i.e., it may be a non-aqueous electrolyte). In addition to containing water, or instead of containing water, the electrolyte may contain one or more organic solvents. For example, the electrolyte may contain acetonitrile, propylene carbonate, ethylene carbonate, dimethylformamide, diethyl carbonate, adiponitrile, and / or dimethyl sulfoxide.

[0088] In some embodiments, the electrolyte described herein comprises one or more salts. The salts may be dissolved in a solvent (e.g., one or more of the solvents described herein) or may form an ionic liquid (e.g., the salts may be liquid at room temperature and room pressure and may be provided without further solvent). The salts may contain one or more ions configured to intercalate and / or be absorbed into the metal-organic structures and / or supercapacitor electrodes described herein. These ions may intercalate (and / or be absorbed into and / or desorbed from) the metal-organic structures and / or supercapacitor electrodes described herein during charging and discharging of the supercapacitor. Such salts may typically contain counterions for these ions (in some embodiments, they may not be configured to intercalate and / or be absorbed into the metal-organic structures and / or supercapacitor electrodes described herein, but in other embodiments, they may be configured to intercalate and / or be absorbed into the metal-organic structures and / or supercapacitor electrodes described herein during the activation process). In some embodiments, the electrolyte comprises one or more ion-deficient salts configured to be intercalated and / or absorbed into the metal-organic structures and / or supercapacitor electrodes described herein. Either type of salt may contain ions transported between the supercapacitor electrodes during charging and discharging to form an ionic current that balances the electron flow also transported between the relevant electrodes. This ionic current can work to maintain charge neutrality throughout the supercapacitor.

[0089] The electrolytes described herein may include salts containing ions having various suitable diameters, lengths, and / or widths. For example, the electrolyte may include salts containing ions having diameters, lengths, and / or widths smaller than the pores of the metal-organic structures described herein and / or smaller than the spacing between the two-dimensional sheets of the metal-organic structures described herein. In some embodiments, the electrolyte includes salts containing ions having diameters, lengths, and / or widths greater than or equal to 0.1 Å, greater than or equal to 0.2 Å, greater than or equal to 0.5 Å, greater than or equal to 0.75 Å, greater than or equal to 1 Å, greater than or equal to 2 Å, greater than or equal to 5 Å, greater than or equal to 7.5 Å, greater than or equal to 10 Å, greater than or equal to 15 Å, or greater than or equal to 20 Å. In some embodiments, the electrolyte comprises a salt containing ions having a diameter, length, and / or width of less than or equal to 25 Å, less than or equal to 20 Å, less than or equal to 15 Å, less than or equal to 10 Å, less than or equal to 7.5 Å, less than or equal to 5 Å, less than or equal to 2 Å, less than or equal to 1 Å, less than or equal to 0.75 Å, less than or equal to 0.5 Å, or less than or equal to 0.2 Å. Combinations of the ranges mentioned above are also possible (e.g., greater than or equal to 0.1 Å and less than or equal to 25 Å). Other ranges are also possible.

[0090] It should be understood that the electrolytes described herein may contain ions having a diameter, length, and / or width within one or more of the above-mentioned ranges when in the form of naked ions (i.e., in a vacuum), and / or ions having a diameter, length, and / or width within one or more of the above-mentioned ranges when in the form of solvated ions (i.e., dissolved in a solvent).

[0091] The electrolyte described in this specification may contain salts having monoatomic cations and / or polyatomic cations. Non-limiting examples of suitable monoatomic cations include H + , alkali metal cations (e.g., Li + , Na + , K + ), alkaline earth metal cations (e.g., Mg 2+ , Ca 2+ ), and post-transition metal cations (e.g., Al 3+ ). Non-limiting examples of suitable polyatomic cations include quaternary ammonium cations (e.g., ammonium cation, tetramethylammonium cation, tetraethylammonium cation, tetrabutylammonium cation, tetraamylammonium cation, tetrahexylammonium cation, tetraheptylammonium cation, tetraoctylammonium cation, tetraethylmethylammonium cation), quaternary phosphonium cations (e.g., phosphonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, tetrabutylphosphonium cation, tetraamylphosphonium cation, tetrahexylphosphonium cation, tetraheptylphosphonium cation, and tetraoctylphosphonium cation), pyrrolidinium cations (e.g., N-methyl-N-butyl-pyrrolidinium, N-methyl-N-methoxyethyl-pyrrolidinium, N-methyl-N-propyl-pyrrolidinium), and imidazolium cations (e.g., 1-ethyl-3-methylimidazolium, 1-butyl-3-methylimidazolium). As can be understood from the above, the electrolyte salt may contain cations having various suitable valences. For example, the electrolyte salt may contain monovalent cations, divalent cations, trivalent cations, and / or tetravalent cations.

[0092] Similarly, the electrolyte described in this specification may contain salts having monoatomic anions and / or polyatomic anions. Non-limiting examples of suitable monoatomic anions are halogen anions (e.g., Cl -) includes. A non-limiting example of a suitable polyatomic anion is SO4. 2- NO3 - ClO4 - CO3 2- , PO4 - , OH - BF4 - PF6 - , and bis(trifluoromethane)sulfonamide anions are included. As can be understood from the above considerations, the electrolyte salt may contain anions with various appropriate valencies. For example, the electrolyte salt may contain monovalent and / or divalent anions.

[0093] As described above, a supercapacitor may include one or more electrodes containing a metal-organic structure, or one or more electrodes lacking a metal-organic structure. Electrodes lacking a metal-organic structure may include a variety of suitable materials, such as carbon (e.g., porous carbon, carbon black, graphite, graphene, carbon nanotubes), carbonitrides, transition metal carbides, metal oxides (e.g., ruthenium oxide, molybdenum oxide, niobium oxide, manganese oxide, nickel oxide, cobalt oxide, iron oxide), metal sulfides (e.g., nickel sulfide, cobalt sulfide, molybdenum sulfide, copper sulfide), metal hydroxides (e.g., nickel hydroxide, cobalt hydroxide), and / or metal nitrides (e.g., vanadium nitride, titanium nitride, tungsten nitride, molybdenum nitride, niobium nitride, gallium nitride). In some embodiments, electrodes lacking a metal-organic structure may take the form of a covalent organic structure or MXene.

[0094] Electrodes lacking a metal-organic structure may act as a cathode (e.g., in the case of electrodes containing carbon, metal oxides, metal sulfides, metal hydroxides, and / or metal nitrides) and / or an anode (e.g., in the case of electrodes containing carbon and / or MXene). Electrodes acting as cathodes typically have a potential greater than -2V relative to the silver wire electrode (e.g., between -2V and 3V), while electrodes acting as anodes typically have a potential less than -2V relative to the silver wire electrode (e.g., between -3V and -2V). However, it should be understood that any of the aforementioned materials may act as either a cathode or an anode when paired with a suitable electrode that acts as the other (e.g., as a cathode when paired with an anode having a lower potential relative to the silver wire electrode, and as an anode when paired with a cathode having a higher potential relative to the silver wire electrode).

[0095] It should also be understood that electrodes lacking a metal-organic structure may be configured to intercalate and / or absorb ions (e.g., electrodes containing carbon polarized to a potential less than or equal to -2.5V or greater than or equal to -2.5V relative to a silver wire electrode), or they may not be configured to intercalate or absorb ions (e.g., electrodes containing carbon polarized by other means). Electrodes lacking a metal-organic structure may be configured to undergo redox reactions during charging and discharging (e.g., electrodes configured to intercalate and / or absorb ions), or they may not be configured to undergo redox reactions during charging and discharging (e.g., electrodes not configured to intercalate and / or absorb ions).

[0096] In some embodiments, the electrodes described herein (e.g., electrodes containing a metal-organic structure, electrodes lacking a metal-organic structure) may further include a current collector. The current collector may be a conductive material that assists in the transport of current to and / or from the electrode during charging and discharging. The current collector may be in the form of a form or other form (e.g., foil, film, disk, matrix, carbon cloth, conductive flexible polymer material). Non-limiting examples of materials that may be used for the current collector include metals (e.g., nickel, gold, platinum), alloys (e.g., stainless steel), and carbon.

[0097] The supercapacitors described herein may have a variety of suitable voltage drops across them. In some embodiments, the voltage drop across the supercapacitor is less than or equal to 4V, less than or equal to 3.5V, less than or equal to 3V, less than or equal to 2.5V, less than or equal to 2V, less than or equal to 1.5V, less than or equal to 1V, or less than or equal to 0.5V. In some embodiments, the voltage drop across the supercapacitor is greater than or equal to 0V, greater than or equal to 0.5V, greater than or equal to 1V, greater than or equal to 1.5V, greater than or equal to 2V, greater than or equal to 2.5V, greater than or equal to 3V, or greater than or equal to 3.5V. Combinations of the ranges mentioned above are also possible (e.g., less than or equal to 4V and greater than or equal to 0V). Other ranges are also possible.

[0098] The potential drop across the supercapacitor may be determined by using a voltmeter.

[0099] In some embodiments, the supercapacitors described herein have advantageously high weight-to-weight capacitance. For example, a supercapacitor may have a weight-to-weight capacitance greater than or equal to 50 F / g, greater than or equal to 75 F / g, greater than or equal to 100 F / g, greater than or equal to 125 F / g, greater than or equal to 150 F / g, greater than or equal to 200 F / g, greater than or equal to 250 F / g, greater than or equal to 300 F / g, greater than or equal to 350 F / g, greater than or equal to 400 F / g, greater than or equal to 450 F / g, greater than or equal to 500 F / g, greater than or equal to 550 F / g, greater than or equal to 600 F / g, greater than or equal to 650 F / g, or greater than or equal to 700 F / g. In some embodiments, the supercapacitor has a specific weight capacitance of less than or equal to 750 F / g, less than or equal to 700 F / g, less than or equal to 650 F / g, less than or equal to 600 F / g, less than or equal to 550 F / g, less than or equal to 500 F / g, less than or equal to 450 F / g, less than or equal to 400 F / g, less than or equal to 350 F / g, less than or equal to 300 F / g, less than or equal to 250 F / g, less than or equal to 200 F / g, less than or equal to 150 F / g, less than or equal to 125 F / g, less than or equal to 100 F / g, or less than or equal to 75 F / g. Combinations of the ranges mentioned above are also possible (for example, greater than or equal to 50 F / g and less than or equal to 750 F / g, greater than or equal to 50 F / g and less than or equal to 400 F / g, or greater than or equal to 100 F / g and less than or equal to 750 F / g). Other ranges are also possible.In some embodiments, a supercapacitor otherwise identical may have a higher specific gravity capacity when it contains an aqueous electrolyte than when it contains a non-aqueous electrolyte (for example, a supercapacitor containing an aqueous electrolyte may have a specific gravity capacity greater than or equal to 100 F / g and less than or equal to 750 F / g, while a supercapacitor containing a non-aqueous electrolyte and otherwise identical may have a specific gravity capacity greater than or equal to 50 F / g and less than or equal to 400 F / g).

[0100] The weight-to-weight capacitance of a supercapacitor may be determined by the following procedure: (1) leaving the supercapacitor undisturbed overnight at room temperature; (2) performing several cyclic voltammetry cycles thereon at a scan rate of 20 mV / s until a stable cyclic voltammetry curve is created; and (3) performing a final cyclic voltammetry cycle thereon at a scan rate of 1 mV / s across the entire 600 mV scan window; and (4) determining the weight-to-weight capacitance by dividing the capacitance measured during the final cyclic voltammetry cycle by the weight of the supercapacitor.

[0101] In some embodiments, the supercapacitors described herein have advantageously high power densities. For example, the supercapacitors have power densities greater than or equal to 0.5 W / g, greater than or equal to 0.75 W / g, greater than or equal to 1 W / g, greater than or equal to 1.25 W / g, greater than or equal to 1.5 W / g, greater than or equal to 2 W / g, greater than or equal to 2.5 W / g, greater than or equal to 3 W / g, greater than or equal to 3.5 W / g, greater than or equal to 4 W / g, greater than or equal to 4.5 W / g It may have a power density of 5 W / g or more, 5.5 W / g or more, 6 W / g or more, 6.5 W / g or more, 7 W / g or more, 7.5 W / g or more, 8 W / g or more, 8.5 W / g or more, 9 W / g or more, or 9.5 W / g or more. In some embodiments, the supercapacitor has a power density of less than or equal to 10 W / g, less than or equal to 9.5 W / g, less than or equal to 9 W / g, less than or equal to 8.5 W / g, less than or equal to 8 W / g, less than or equal to 7.5 W / g, less than or equal to 7 W / g, less than or equal to 6.5 W / g, less than or equal to 6 W / g, less than or equal to 5.5 W / g, less than or equal to 5 W / g, less than or equal to 4.5 W / g, less than or equal to 4 W / g, less than or equal to 3.5 W / g, less than or equal to 3 W / g, less than or equal to 2.5 W / g, less than or equal to 2 W / g, less than or equal to 1.5 W / g, less than or equal to 1.25 W / g, less than or equal to 1 W / g, or less than or equal to 0.75 W / g. Combinations of the ranges mentioned above are also possible (for example, greater than or equal to 0.5 W / g and less than or equal to 10 W / g). Other ranges are also possible.

[0102] The power density of the supercapacitor may be determined by performing the first three steps to determine the weight specific capacity described elsewhere in this specification and then dividing the power measured during the final cyclic voltammetry cycle by the weight of the supercapacitor to determine the power density.

[0103] For convenience, certain terms used in this specification, the examples, and the appended claims are listed herein. The definitions of specific functional groups and chemical terms are described in more detail below. For the purposes of the present invention, chemical elements are identified according to the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75th Ed., inside the back cover, and specific functional groups are generally defined as described therein. Further, general principles of organic chemistry as well as specific functional moieties and reactivities are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito: 1999.

[0104] As used herein, the term "aliphatic" includes both saturated and unsaturated, non-aromatic, straight-chain (i.e., unbranched), branched, acyclic, and cyclic (i.e., carbocyclic) hydrocarbons, optionally substituted with one or more functional groups. As will be understood by those skilled in the art, "aliphatic" is intended herein to include, but not be limited to, alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, and cycloalkynyl moieties. Thus, as used herein, the term "alkyl" includes straight-chain, branched, and cyclic alkyl groups. Similar expressions apply to other general terms such as "alkenyl", "alkynyl", and the like. Further, as used herein, the terms "alkyl", "alkenyl", "alkynyl", and the like encompass both substituted and unsubstituted groups. In certain embodiments, as used herein, "aliphatic" is used to denote an aliphatic group (cyclic, acyclic, substituted, unsubstituted, branched, or unbranched) having from 1 to 20 carbon atoms. Substituents of the aliphatic group include, but are not limited to, any of the substituents described herein that result in the formation of a stable moiety (e.g., aliphatic, alkyl, alkenyl, alkynyl, heteroaliphatic, heterocyclic, aryl, heteroaryl, acyl, oxo, imino, thioxo, cyano, isocyano, amino, azide, nitro, hydroxyl, thiol, halo, aliphatic amino, heteroaliphatic amino, alkylamino, heteroalkylamino, arylamino, heteroarylamino, alkylaryl, arylalkyl, aliphatic oxy, heteroaliphatic oxy, alkyloxy, heteroalkyloxy, aryloxy, heteroaryloxy, aliphatic thioxy, heteroaliphatic thioxy, alkylthioxy, heteroalkylthioxy, arylthioxy, heteroarylthioxy, acyloxy, and the like, each of which may or may not be further substituted).

[0105] The term "alkyl" refers to the radical of a saturated aliphatic group, including linear alkyl groups, branched alkyl groups, cycloalkyl (alicyclic) groups, alkyl-substituted cycloalkyl groups, and cycloalkyl-substituted alkyl groups. Alkyl groups may be substituted as needed, as will be further described below. Examples of alkyl groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, 2-ethylhexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and similar groups. A "heteroalkyl" group is an alkyl group in which at least one atom is a heteroatom (e.g., oxygen, sulfur, nitrogen, phosphorus, etc.) and the remaining atoms are carbon atoms. Examples of heteroalkyl groups include, but are not limited to, alkoxy, poly(ethylene glycol)-, alkyl-substituted amino, tetrahydrofuranyl, piperidinyl, morpholinyl, etc.

[0106] The terms “alkenyl” and “alkynyl” refer to unsaturated aliphatic groups similar to the alkyl groups described above, but each containing at least one double or triple bond. “Heteroalkenyl” and “heteroalkynyl” refer to alkenyl and alkynyl groups described herein in which one or more atoms are heteroatoms (e.g., oxygen, nitrogen, sulfur, and similar).

[0107] The term "aryl" refers to an aromatic carbocyclic group having a monocyclic (e.g., phenyl), polycyclic (e.g., biphenyl), or multiple fused ring, at least one of which is aromatic (e.g., 1,2,3,4-tetrahydronaphthyl, naphthyl, anthryl, or phenanthryl), all of which may be substituted as appropriate. A "heteroaryl" group is an aryl group in which at least one ring atom of the aromatic ring is a heteroatom, and the remaining ring atoms are carbon atoms. Examples of heteroaryl groups include furanyl, thienyl, pyridyl, pyrrolyl, N lower alkylpyrrolyl, pyridyl N oxide, pyrimidyl, pyrazinyl, imidazolyl, indolyl, and similar groups, all of which may be substituted as appropriate.

[0108] The terms "amine" and "amino" refer to both unsubstituted and substituted amines, and are parts that can be represented, for example, by the general formula: N(R')(R”)(R'''), where R', R'', and R''' each independently represent a group recognized by the law of valence.

[0109] The terms "acyl," "carboxyl group," or "carbonyl group" are recognized in the art, and the general formula is: [ka] (In the formula, W is H, OH, O-alkyl, O-alkenyl, or a salt thereof) The formula may include parts that can be represented by the following: When W is an O-alkyl group, the formula represents an "ester". When W is an OH group, the formula represents a "carboxylic acid". In general, when the oxygen atom in the above formula is replaced by sulfur, the formula represents a "thiol carbonyl" group. When W is an S-alkyl group, the formula represents a "thiol ester". When W is an SH group, the formula represents a "thiol carboxylic acid". On the other hand, when W is an alkyl group, the above formula represents a "ketone" group. When W is hydrogen, the above formula represents an "aldehyde" group.

[0110] As used herein, the terms “heteroaromatic” or “heteroaryl” mean a monocyclic or polycyclic heteroaromatic ring (or its radical) comprising carbon atom ring members and one or more heteroatom ring members (e.g., oxygen, sulfur, or nitrogen). Typically, a heteroaromatic ring has 5 to about 14 ring members, with at least one ring member being a heteroatom selected from oxygen, sulfur, and nitrogen. In another embodiment, the heteroaromatic ring may be a 5 or 6-membered ring and contain 1 to about 4 heteroatoms. In yet another embodiment, the heteroaromatic ring system may have 7 to 14 ring members and contain 1 to about 7 heteroatoms. Typical heteroaryls include pyridyl, furyl, thienyl, pyrrolyl, oxazolyl, imidazolyl, indolidinyl, thiazolyl, isoxazolyl, pyrazolyl, isothiazolyl, pyridadinyl, pyrimidinyl, pyrazinyl, triazinyl, triazolyl, pyridinyl, thiadiazolyl, pyrazinyl, quinolyl, isoquinolyl, indazolyl, benzoxazolyl, benzofuryl, benzothiazolyl, indolidinyl, imidazopyridinyl, isothiazolyl, tetrazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzothiadiazolyl, benzoxadiazolyl, carbazolyl, indolyl, tetrahydroindolyl, azaindolyl, imidazopyridyl, knizaolinyl, purinyl, pyrrolo[2,3]pyrimidyl, pyrazolo[3,4]pyrimidyl, benzo(b)thienyl, and similar. These heteroaryl groups may be substituted with one or more substituents, as needed.

[0111] The term “substituted” is intended to include all permissible substituents of an organic compound, and “permissible” is in the context of the chemical laws of valence known to those skilled in the art. In some cases, “substituted” may generally refer to the substitution of hydrogen in substituents described herein. However, as used herein, “substituted” does not include substitutions and / or modifications of key functional groups that thereby identify the molecule, such as when a “substituted” functional group becomes a different functional group through substitution. For example, “substituted phenyl” in this definition must still contain the phenyl moiety and cannot be modified by substitution such as becoming a heteroaryl group, such as pyridine. In a broad range of embodiments, permissible substituents of an organic compound include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and non-aromatic substituents. Exemplary substituents include, for example, those described herein. Permissible substituents may be one or more, the same or different with respect to a suitable organic compound. For the purposes of the present invention, the heteroatom, such as nitrogen, may have a hydrogen substituent and / or any acceptable substituent of the organic compound described herein that satisfies the valency of the heteroatom. The present invention is not limited in any way by the acceptable substituent of the organic compound.

[0112] Examples of substituents include, but are not limited to, alkyl, aryl, aralkyl, cyclic alkyl, heterocycloalkyl, hydroxy, alkoxy, aryloxy, perhaloalkoxy, aralkoxy, heteroaryl, heteroaryloxy, heteroarylalkyl, heteroaralkoxy, azide, amino, halogen, alkylthio, oxo, acyl, acylalkyl, carboxyester, carboxyl, carboxamide, nitro, acyloxy, aminoalkyl, alkylaminoaryl, alkylaryl, alkylaminoalkyl, alkoxyaryl, arylamino, aralkylamino, alkylsulfonyl, carboxamidealkylaryl, carboxamidearyl, hydroxyalkyl, haloalkyl, alkylaminoalkylcarboxy, aminocarboxamidealkyl, alkoxyalkyl, perhaloalkyl, arylalkyloxyalkyl, and similar. [Examples]

[0113] (Example 1) This embodiment describes a novel lithium-ion high-capacity and low equivalent series resistance (ESR) electrode utilizing a highly conductive porous two-dimensional metal-organic structure (2D-MOF). In this two-dimensional metal-organic structure, charge is stored via the insertion of lithium-ion into the 2D-MOF within the pseudo-circular pores of the structure. The electrode has a capacity of 475 F / g and a measured ESR of 0.17 ohms in an aqueous LiCl electrolyte. This performance is thought to be related to the structure and chemical composition of the 2D-MOF, which includes both an aperture small enough for efficient lithium-ion insertion and conductivity high enough to provide low ESR.

[0114] The conductive 2D-MOF used in this example is copperbenzenehexathiol (Cu3BHT1), in which the benzenehexathiol moiety is coordinated to the copper ion. This 2D-MOF is 10m 2Although it shows a BET surface area of ​​approximately / g, the true surface area of ​​this 2D-MOF is likely to be larger than this value. Cu3BHT1 contains pseudo-triangular pores whose boundaries are formed by copper and sulfur atoms (see Figure 9A), which are too small for gas probes (e.g., N2) used during BET measurements to penetrate, but are considered to be sufficiently large, especially in supercapacitor applications.

[0115] For this reason, this embodiment intends to use Cu3BHT1 and structural analogues having the following characteristics: (1) conductive ligands such as conjugated aromatic ligands; (2) metal ions; and (3) pores having a diameter suitable for insertion of lithium or other ions, e.g., pores larger than or equal to 0.3 nm and smaller than or equal to 0.33 nm, one or more of these. 2D-MOFs suitable for intercalating and / or absorbing other alkali ions and / or alkaline earth metal ions are also intended, as with the use of aqueous and non-aqueous solvents to solubilize such ions.

[0116] Figure 9B shows the cyclic voltammetry (CV) curves of the Cu3BHT1 electrode in aqueous LiCl electrolyte. These curves show two distinct events at a sweep of 1 mV / sec, one at -0.66 V and the other at -0.35 V. While not adhering to any particular theory, these events are thought to be related to the interaction between lithium ions and 2D-MOFs, and such interactions are thought to contribute to the high capacity measurements. These same interactions can be observed in the constant current charge-discharge sweep shown in Figure 9C. The maximum capacity recorded for the Cu3BHT1 electrode was 475 F / g at a cycling rate of 1 mV / sec. This electrode also showed good capacity retention, with capacity values ​​greater than 100 F / g recorded at a cycling rate of 10 mV / sec (inset in Figure 9B). The stability of the capacity was confirmed by constant current charge and discharge. The Cu3BHT1 electrode showed a retention rate of 90% of its initial capacity after 5000 charge and discharge cycles at a current density of 5 A / g.

[0117] It should be noted that the measured capacity may vary with ramp speed: Figure 10 shows further data obtained at 10 mV / sec in the presence of NaCl solution, where the Cu3BHT1 electrode showed a capacity of 290 F / g.

[0118] Further experiments were conducted to collect electrochemical impedance spectroscopy (EIS) Nyquist plots for the Cu3BHT1 electrode. These plots were collected over a 20-minute period by performing the following steps: (1) applying a voltage of -0.1V to the electrode; (2) reducing the applied voltage to the electrode to -0.6V; and (3) increasing the applied voltage to the electrode back to the original -0.1V (Figure 11A). The Nyquist plot for the electrode contains three semicircles: one each at high, medium, and low frequencies.

[0119] During the voltage sweep, the position of the ESR at the smallest semicircle's high-frequency end shifted upward from 0.15 ohms at -0.2V to 0.20 ohms at -0.6V. This ESR then shifted back to its original 0.15 ohms after returning to -0.2V.

[0120] The radius of the semicircle at medium frequencies varied from 1.4 to 1.7 ohms during the same voltage sweep described above, showing variability that is thought to be related to the change in charge transfer resistance.

[0121] The low-frequency semicircle showed the greatest variation over the voltage sweep described above: it changed from 20 ohms at -0.2V to 675 ohms at -0.6V. From Figure 11A, it is clear that the shape of the low-frequency semicircle changed most rapidly between -0.4V and -0.2V and less rapidly in the region around -0.6V. The low-frequency semicircle is thought to be related to the resistivity of the electrolyte: Li into the electrode + The increased introduction of ions is thought to raise its resistance, leading to increased ESR and charge transfer resistance. Free Li in the electrolyte + The amount of ions is Li into the electrode. +It is also conceivable that it decreases during charging due to the intercalation of ions, increasing the resistivity of the electrolyte.

[0122] The powder X-ray diffraction pattern of Cu3BHT1 obtained at the voltage at which the peak in the CV trace occurs reveals no change in its unit cell and no Li + insertion into and removal from it, suggesting that this material did not experience mechanical stress (Figure 11B). Advantageously, this also suggests that the charge and discharge of Cu3BHT1 can be carried out without mechanical stress.

[0123] Figure 12 shows the cyclic voltammetry curve for the Cu3BHT1 electrode in the presence of an electrolyte containing acetonitrile and LiPF6. This cyclic voltammetry curve was obtained at 20 mV / sec and reveals the capacitance for the Cu3BHT1 electrode of 254 F / g in the electrochemical window from 0.2 V to -1.2 V compared to a silver wire. Figure 12 shows that the Cu3BHT1 electrode can also be suitable in supercapacitors containing non-aqueous and / or organic electrolytes.

[0124] The Cu3BHT1 electrode was fabricated by pressing the synthesized 2D-MOF so that pellets were formed. Either Ni foam or gold current collectors were used to support the Cu3BHT1 electrode, and both enabled the electrode to show the same CV shape during the above tests. The CV peak absolute voltage value shifted slightly when other test conditions were changed (e.g., shifted from the measurement performed in a beaker to the measurement performed in a stainless-steel cell), but these shifts were thought to be due to the different cell geometries and different relative masses of the 2D-MOF electrode and the carbon counter electrode under these different test conditions. For a given experimental setup, the results were consistent throughout several different cells tested over several weeks and formed from various batches of Cu3BHT1.

[0125] (Example 2) This example describes the performance of an electrode containing a nickelbenzene hexathiol (Ni3BHT1) metal-organic structure.

[0126] Figure 13A shows a schematic diagram of the Ni3BHT1 structure, which forms a two-dimensional sheet containing pores.

[0127] Ni3BHT12D-MOF exhibits favorable volume values ​​in the presence of aqueous electrolytes containing LiCl and / or NaCl, as shown in Figures 13B-13C (showing cyclic voltammetry curves obtained at 2 mV / sec and specific volume as a function of scan rate, respectively). Ni3BHT12D-MOF contains the following ion: Mg 2+ , K + , Al3 + SO4 2- CO3 - , and NO3 - It is also conceivable that it could have been used in a supercapacitor containing an aqueous electrolyte that included one or more of these types.

[0128] Ni3BHT12D-MOF exhibits favorable volume values ​​even in the presence of non-aqueous electrolytes, and examples of this are detailed below.

[0129] Figures 14A–14C show cyclic voltammetry curves for Ni3BHT1 in electrolytes containing acetonitrile and LiPF6 at various scan rates and potential windows. Figure 14D shows the specific volume extracted from this data as a function of scan rate. It should be noted that the cyclic voltammetry curves do not show any distinct redox peaks, and therefore it is possible to induce intercalation of lithium ions into the Ni3BHT1 electrode without a redox reaction between lithium ions and Ni3BHT12D-MOF.

[0130] Figure 15 shows cyclic voltammetry curves for Ni3BHT1 in electrolytes containing acetonitrile and NaPF6, performed at a scan rate of 20 mV / sec, illustrating the suitability of this 2D-MOF for use in supercapacitor electrodes configured to intercalate sodium ions.

[0131] Figure 16 shows the cyclic voltammetry curves for Ni3BHT1 in electrolytes containing ethylene carbonate, dimethyl carbonate, and LiPF6, performed at a scan rate of 20 mV / sec, demonstrating the suitability of this 2D-MOF for use in supercapacitor electrodes containing other types of non-aqueous electrolytes.

[0132] Figures 17A–17D show cyclic voltammetry curves for Ni3BHT1 in electrolytes containing acetonitrile and various salts. These cyclic voltammetry curves, obtained at 10 mV / s, demonstrate that Ni3BHT1 can intercalate larger cations (such as those typically found in ionic liquids) in addition to the alkali metal cations mentioned above. In the presence of LiPF6, the cyclic voltammetry curve for Ni3BHT1 (Figure 17A) has a nearly rectangular shape, indicating ion intercalation into its interior. However, instead, larger EMIMs are observed. + , TEA + , and TBA + The cyclic voltammetry curve for Ni3BHT1 in the presence of a cation-containing salt has a sharp shape.

[0133] While not adhering to any particular theory, cyclic voltammetry curves with shapes containing lower current intensities at greater polarization (-1V to -2V) (e.g., the sharper shapes at greater polarization, as shown in Figures EAB-EAD) suggest that 2D-MOFs have some surface area inaccessible to larger ions. In Ni3BHT1, it is thought that larger ions may not be able to penetrate between the two-dimensional sheets. The spacing between the two-dimensional sheets in Ni3BHT1 is approximately 0.35 nm, which is Li + and Na + Larger than the diameter of the cation, EMIM + , TEA + , and TBA + These are smaller than the diameter of the cation (0.7, 0.68, and 0.82 nm, respectively).

[0134] Figures 18A-18B show the cyclic voltammetry curves for Ni3BHT1 on a potential window, including both positive and negative portions relative to the silver wire reference electrode. Three cycles were performed at 20 mV / sec: in the first cycle, a negative potential was applied to the 2D-MOF during the cycle; in the second cycle, a positive potential was applied to the 2D-MOF during the cycle; and the third cycle was identical to the first cycle.

[0135] The cyclic voltammetry curve from the first cycle has a sharp shape, as described above. However, the shape from the third cycle onward was more rectangular. It is thought that the application of a positive charge to the 2D-MOF during the second cycle caused anions from the salt dissolved in the electrolyte to intercalate into its interior, and this intercalation increased the average spacing between the two-dimensional sheets inside. This may have made it possible to enhance the intercalation of larger cations into the 2D-MOF during the third cycle.

[0136] (Example 3) This embodiment describes the performance of a supercapacitor comprising an anode containing a nickelbenzene hexathiol (Ni3BHT1) metal-organic structure having the structure shown in Figure 13A, and a cathode containing porous carbon. The supercapacitor further contains an electrolyte comprising 1 M LiPF6 in acetonitrile.

[0137] Figure 19A shows the cyclic voltammetry curves for a supercapacitor performed at 10 mV / s. These curves exhibit a stable rectangular shape in voltage windows of 2 V, 2.2 V, and 2.5 V.

[0138] Figure 19B shows constant current charge-discharge sweeps for a supercapacitor. These constant current charge-discharge sweeps were performed with a current of 2 A / g and cyclically operated between voltages of 0V to 2V, 0V to 2.2V, and 0V to 2.5V.

[0139] Figure 19C shows the cyclic voltammetry curves for a supercapacitor performed at 10 mV / s. These curves demonstrate reversibility within a voltage window up to 3 V. However, cyclic operation within a voltage window 2.5 V over yields the presence of a distorted shape.

[0140] Figure 19D shows the specific capacitance of a supercapacitor as a function of time when cyclically operated at 2A / g at voltages between 0V and 2.5V.

[0141] (Example 4) This embodiment describes a method for synthesizing a metal-organic structure having a structure suitable for use as an electrode for a supercapacitor.

[0142] Figure 20A shows a schematic diagram of the method for synthesizing benzene hexathiol ligands.

[0143] Figure 20B shows a schematic diagram of a method for synthesizing a metal-organic structure from a benzene hexathiol ligand and a metal chloride to form a metal-organic structure containing a metal ion from a metal chloride to which a benzene hexathiol ligand is coordinated.

[0144] (Example 5) Supercapacitors (SCs) emerged as reliable, fast-charging electrochemical energy storage devices that offer high power density. Nevertheless, their relatively low energy density still limits their use. This example describes a novel non-porous CP, (Ni3(benzene hexathiolate)(Ni3BHT1), exhibiting high conductivity exceeding 500 S / m. When used as an electrode for supercapacitors, Ni3BHT1 exhibits conductivity of 245 F / g and 426 F / cm² in non-aqueous electrolytes. 3 It delivers excellent specific capacity. Structural and electrochemical studies have shown that Li is present between the 2D layers of Ni3BHT1. + Regarding preferred performance for pseudocapacitance intercalation of ions.

[0145] Synthetic and structural characterization Microcrystalline samples of Ni3BHT1 were obtained by the reaction of benzenehexathiol, C6S6H6, with NiCl2·6H2O in degassed methanol under anaerobic conditions at room temperature for 24 hours. After isolation from the mother liquor, Ni3BHT1 showed no weight loss at temperatures below 200°C, and its conductivity was maintained in air for at least 6 months (Figure 21). The powder X-ray diffraction (PXRD) pattern of as-synthesized Ni3BHT1 did not match the pattern of Ni3(BHT)2, but instead resembled the pattern of Cu3BHT1 (Figure 22). Further analysis after limited-field electron diffraction (SAED) revealed unit cell parameters a=14.16 Å, b=8.86 Å, c=3.45 Å, α=90°, β=99.7°, and γ=90°, which are indeed similar to those of Cu3BHT1 (Figures 23-26). In summary, PXRD and SAED data suggest that Ni3BHT1 is a new phase that is very similar to Cu3BHT1, and is a planar quadrilateral Ni 2+This suggests that the ionized 2D layer is bonded to the BHT ligand, which is surrounded by four S atoms and six Ni atoms in a planar quadrilateral coordination. These form a dense arrangement, in contrast to the more open hexagonal honeycomb structure of Ni3BHT2 (Figure 26). Elemental analysis revealed C and S content of 19.5% and 44.6%, respectively, which is close to the predicted values ​​for the chemical composition of Ni3C6S6 for Ni3BHT1, confirming that the ligand does not undergo desulfurization during the reaction. Attempts to determine the Ni content after digestion appeared to be hampered by the low solubility of NiS.

[0146] The bulk physical properties of Ni3BHT1 were studied using scanning electron microscopy (SEM), N2 gas sorption analysis, and van der Pauw conductivity measurements. SEM images revealed rod-like structures with lengths greater than 100 nm and diameters of several tens of nanometers (Figure 27). N2 sorption analysis yielded approximately 25 m, consistent with the nonporous properties predicted for Ni3BHT1. 2 A Brunauer-Emmett-Teller (BET)SSA with a low / g was determined (Figure 28). The variable temperature conductivity of the pressurized Ni3BHT1 pellet demonstrated excellent conductivity of approximately 500 S / m at 298 K and a constant decrease with decreasing temperature, as observed for several other bulk phases of 2D MOFs (Figure 29). Overall, the 2D layered structure of Ni3BHT1 and its high conductivity and thermal stability helped evaluate its performance in supercapacitors. Electrochemical analysis was performed using a 1M lithium hexafluorophosphate (LiPF6) / MeCN electrolyte, which is thought to have a sufficiently small cation size to allow for possible intercalation between Ni3BHT1 layers.

[0147] Electrochemical performance of supercapacitors Cyclic voltammetry (CV) of Ni3BHT1 powder pressurized on Ni foam was performed in a three-electrode cell using sufficiently large porous carbon as the counter electrode and an Ag line as a pseudoreference. CV curves obtained over a gradually increasing potential window up to 1.7 V showed distorted rectangular curves and did not exhibit a clear Faraday process (Figure 30). Stable rectangular voltammograms were observed even when the scan rate was reduced to approximately 0.5 mV / sec (Figures 31A and B), however, scans above -1.7 V relative to the open-circuit potential (OCP) resulted in rapid current decay after multiple cycles (Figure 32). Overall, the CV response indicates a capacitive charge storage process in Ni3BHT1 and also identifies a safe working potential window of 1.7 V. Ni3BHT1 is rated at 245 F / g and 426 F / cm². 3 The high specific capacitance of Ni3BHT1 is observed at a scan speed of 3 mV / sec, which is unusually high for a material with such a low surface area as Ni3BHT1. In fact, given its low surface area, the high specific capacitance of Ni3BHT1 is unlikely to be due to ideal bilayer charge storage. An alternative mechanism is a pseudocapacitance mechanism based on intercalation.

[0148] In other words, investigating the mechanism that causes the high capacitance of Ni3BHT1 means going through electrochemical dynamics studies to evaluate the properties of ion sorption to electrodes. The capacitive contribution in Ni3BHT1 is i(V) / υ with respect to a certain range of scan speeds at three different potentials. 1 / 2 vs υ 1 / 2The current was analyzed by plotting it (Figures 33-34). The slopes of these curves indicate that the main capacitive contributions were 80%, 78%, and 76% at -1.2, -1.5, and -1.7 V versus OCP, respectively, suggesting surface-controlled ion sorption in Ni3BHT1. The specific capacities calculated from these curves reached high values ​​of 195, 124, and 85 F / g at scan rates of 7, 14, and 28 mV / s, respectively (Figure 35). Long-term cyclic operation studies of Ni3BHT1 at a fast scan rate of 30 mV / s (discharge in 56 seconds) across various potential windows showed retention of over 80% after 8,000 cycles (Figure 36), while cyclic operation at the widest window of 1.7 V reduced the capacitance retention to 70% after 2,000 cycles (Figure 37).

[0149] Electrochemical impedance spectra (EIS) were recorded using OCP under various cathodes to analyze ion transport in Ni3BHT1 under dynamic conditions (Figure 38). The EIS curves showed an extended 45° Warburg region in the mid-frequency range and a deviation of intensity from the vertical in the lower-frequency range, which was consistent with the non-ideal capacitive behavior typically associated with limited ion transport in electrode materials. Furthermore, closer examination of the high-frequency range revealed an increase in semicircular diameter with stronger polarization (inset, Figure 38), suggesting the possibility of a charge transfer mechanism typical of pseudocapacitive electrodes in progress.

[0150] The role of electrolytic ion size Next, experiments were conducted to determine whether Ni3BHT1 exhibits intercalation-based pseudocapacitance. For this purpose, electrolyte salts with cations and anions of various sizes were used: tetraethylammonium hexafluorophosphate (NEt4PF6), tetraethylammonium tetrafluoroborate (NEt4BF4), and tetrabutylammonium tetrafluoroborate (NBu4BF4). A comparison of the CV curves obtained for these electrolytes is shown below. +With tetraalkylammonium (TAA) cations, a very low current was demonstrated (Figure 39), and accordingly, a lower capacity of approximately 30 F / g compared to 227 F / g with Li+ (Figure 40). By changing the anion and comparing NEt4PF6 with NEt4BF4, very similar CVs were obtained (Figure 39), suggesting that some difference in behavior is caused by the cation, and accordingly the ion sorption process is mainly driven by the cation. The CV in the TAA electrolyte further shows a nearly flat shape, and the current approaches zero after a cathode-like scan from the OCP. The observed ion sieving behavior may be due to its ordered 2D layer structure, where only ions smaller than the interlayer spacing are intercalated. In fact, Li + The ions are considered small enough to intercalate, and their response in the low-frequency range of the EIS deviates significantly from the ideal vertical line, suggesting that even larger TAAs are too bulky to intercalate. + This is different from the case of cations (Figure 41A).

[0151] Overall, the electrochemical studies support the inference that ion sorption in Ni3BHT1 is influenced by cation size, and that ion intercalation into the 2D layer affects the total capacity. Ni3BHT1 showed a steady-state decrease in performance when discharged for less than 3 minutes (Figure 41B). This, along with the clear deviation from the ideal vertical line at low EIS frequencies predicted for pseudocapacitive materials, indicates that ion transport was hindered at high discharge rates.

[0152] Characterization of electrode processes The structural and compositional evolution of Ni3BHT1 under potential bias was investigated using various ex situ X-ray and solid-phase nuclear magnetic resonance (SSNMR) spectroscopy techniques. PXRD patterns of negatively polarized Ni3BHT1 electrodes cyclically operated in 1M LiPF6 / MeCN demonstrated good retention of crystallinity, highlighting the stability of Ni3BHT1 under electrochemical conditions (Figure 42).

[0153] Ni3BHT1 samples prepared as if immersed in an electrolyte or negatively polarized with SC 7 By comparing the Li SSNMR spectra, we can see the ion sorption under polarization. 7 Various chemical environments for Li were identified. To provide a point of comparison, similar tests were performed with Ni3HITP2 (HITP = 2,3,6,7,10,11-heximinotriphenylene), suggesting that 2D porous MOFs adsorb ions within their micropores. 7 The Li SSNMR spectra showed strong isotropic peaks at approximately 0 ppm for both materials under all conditions (Figures 43 and 44). These peaks indicate Li associated with the particle or pore surface. + The ions were assigned. One notable difference is the asymmetry observed with respect to the polarized Ni3BHT1 sample at approximately 3 ppm, which is even more clearly shown in its satellite peaks at approximately -70 and -73 ppm (inset, Figure 43). The different chemical shifts in the polarized Ni3BHT1 sample are clearly different ionic, having similar isotropic chemical shifts but clearly different nuclear quadrupole coupling interactions, due to the small diamagnetic chemical shift range of lithium. 7 It is possible that it exhibits a Li chemical environment. Ni3HITP2 exhibits micropores, and therefore bilayer ion adsorption is possible, 7 The Li SSNMR spectrum shows a single Gaussian resonance (Figure 44). Additional 7 The Li adsorption site is determined by interlacing Li between 2D sheets according to electrochemical data. + It is thought to originate from ions.

[0154] X-ray absorption spectroscopy (XAS) is thought to demonstrate that the pseudocapacitive behavior of Ni3BHT1 is not Ni-based. Near-field X-ray absorption spectroscopy (XANES) at the Ni-K edge revealed that the edge and pre-edge energies were 8.346 keV and 8.334 keV for untreated and polarized Ni3BHT1, respectively, which is thought to indicate that the 2+ oxidation state of Ni persisted during supercapacitor operation (Figures 45 and 46). Furthermore, analysis of local coordination around Ni from X-ray absorption fine structure (EXAFS) revealed that the Ni coordination numbers were essentially identical, at 4 (±0.4) and 3.7 (±0.4) before and after polarization (Figures 47-48). Similarly, the Ni-S bond length in Ni3BHT1 remained largely unchanged, but a slight decrease from 2.16 (±0.02) to 2.13 (±0.02) Å after polarization suggests an increase in electron density at the S atom. These observations suggest that the redox process is not metal-based, but rather ligand-based. In fact, high-resolution X-ray photoelectron spectroscopy (XPS) shows that the C 1s and Ni 2p peaks are unaffected by polarization, with the only observable change being in the S 2p peak (Figures 50-52). In particular, 2 p1 / 2 and 2 p3 / 2 Deconvolution of the S signal to various chemical components with a doublet structure identifies the loss of the SH component and the emergence of the S-Li component after polarization, indicating the reduction of Li+ associated with the electronegative S moiety and subsequent intercalation (Figures 53-54). In particular, the observed redox process is thought to differentiate Ni3BHT1 from other transition metal-based pseudocapacitive materials that access numerous oxidation states of metal ions (Ru, Nb, or Mo) during intercalation. Unfortunately, the extended conjugated structure on the metal-organic structure makes it impossible to elucidate the precise changes in the oxidation states of the ligands. Nevertheless, the high specific capacitance and large reduction potential window due to intercalation pseudocapacitance identify Ni3BHT1 as a promising anode for the fabrication of high-voltage asymmetric supercapacitors.

[0155] conclusion In summary, despite its lack of porosity, Ni3BHT1 is a promising electrode material for supercapacitors, demonstrating a high specific capacitance of 245 F / g over a large reduction potential window of 1.7 V. Extensive electrochemical analysis supported the inference that such high capacitance in Ni3BHT1 is made possible by an intercalation-based ion sorption mechanism. A schematic of this process is shown in Figure 55.

[0156] material and method NiCl2·6H2O was purchased from Sigma-Aldrich and used without further purification. Methanol and MeCN were purchased from VWR and collected from an alumina column solvent purification system. Methanol was degassed overnight indoors using N2 before Ni3BHT1 synthesis. All electrolyte salts, LiPF6, and tetraalkylammonium salts were purchased from Sigma-Aldrich or Beantown Chemicals and used without further purification. Activated carbon was prepared as a thin film by repeatedly kneading and rolling a mixture of activated carbon slurry, acetylene black, and PTFE solution with ethanol in an 8:1:1 ratio. The prepared films were dried overnight at 120°C and then used in a supercapacitor.

[0157] Synthesis of Ni3BHT1 132 mg (0.555 mmol) of NiCl2·6H2O was first dissolved in 100 mL of degassed methanol under a nitrogen atmosphere. BHT powder (50 mg, 0.185 mmol) was slowly added to the solution over 30 minutes, and the mixture was then reacted at room temperature for 24 hours. The resulting powder was filtered, purified twice with water and ethanol, and dried at 100°C under dynamic vacuum for 12 hours. Yield: 73 mg, 90%.

[0158] Elemental analysis was performed by Robertson Microlit Laboratories, NJ, USA, using combustion and titration techniques. The obtained data were fitted using ethanol and water as solvent residues in the material. Predicted values: C: 19.43%, S: 44.41%, H: 1.61%. Observed values: C: 19.54%, S: 44.66%, H: 1.56%.

[0159] Figure 56 shows a schematic representation of the synthesis of Ni3BHT1.

[0160] conductivity The conductivity of Ni3BHT1 is 3.0 tons-ft / cm³. 2 Measurements were taken using the four-point van der Pauw method on a 7mm diameter pellet that was pressurized. A Keithley 2450 source meter was used as the current source, and a Keithley 2182A unit was used as the voltmeter.

[0161] Electrochemical characterization and analysis All electrochemical measurements were performed using a Biologic VSP-300 potentiostat. EIS measurements were performed using multiple sinusoidal signals of magnitude 10mV over a wide frequency range of 10mHz to 200kHz. Specific weight, specific capacitance (C) g ) to, equation: Cg = ((∫I.dV) / (m.υ.dV)) (In the formula, m = mass of the working electrode, dV = discharge potential window, and υ = scan speed) The volumetric specific capacity (C) was calculated from the discharge sequence of the 3-electrode CV curve using [the specified method]. v ) is C g Electrode density (1.74 g / cm³) 3 The calculation was performed by multiplying by ). The CV at various scan speeds was compared by plotting its speed-normalized current: the current was divided by the corresponding scan speed.

[0162] Instrumentation and sample preparation Powder X-ray diffraction (PXRD) patterns were recorded using a Bruker D8 Advance diffractometer equipped with a Gobel mirror, a rotating sample stage, a LynxEye detector, and a Cu Kα(λD 1.5405) X-ray source in a θ=2θ Bragg-Brentano geometry. An anti-scattering slit (2 mm) and a replaceable detector slit (8 mm) were used. The tube voltage and current were 40 kV and 40 mA, respectively. A knife-edge attachment was used to remove scattering at low angles. Samples for PXRD were prepared by placing electrodes or powders on a zero-background silicon (510) crystal plate. Polarized Ni3BHT1 electrodes were prepared by pressurizing Ni3BHT1 powder on Ni foam and polarizing it in a three-electrode cell. The fabricated cell was first left overnight, then cycled for 100 cycles at a scan speed of 10 mV / sec, held at -1.7 V vs OCP for 5 minutes, and then disassembled.

[0163] Selected-field electron diffraction (SAED) images were obtained using a JEOL-2100 and manipulated with an accelerating voltage of 200 kV. Samples were drop-cast from powder dispersed in methanol onto a Cu TEM grid. Scanning electron microscopy (SEM) images were recorded using a Zeiss Supra 55VP FEG SEM with an InLens detector at an operating voltage of 3 kV. Nitrogen gas adsorption isotherms were measured using a Micromeritics ASAP 2020 surface area and porosity analyzer with a liquid nitrogen bath (77 K). Samples were heated to 90°C for 24 hours under a vacuum of 0.2 mtorr and then analyzed. Thermogravimetric analysis (TGA) was performed on a platinum pan using a TA instrument Q500 thermogravimetric analyzer at a heating rate of 1°C / min under a nitrogen gas flow of 10 mL / min.

[0164] solid phase 7 Li NMR experiments using a Bruker NEO 500 (Bo=11.75T, 500MHz) equipped with a 4mm dual-resonance HX Magic Angular Rotation (MAS) Bruker NMR probe. 1The analysis was performed using an NMR spectrometer. The powdered sample was packed into a 4 mm odZrO2 NMR rotor and closed with a Kel-F cap. NMR data were collected using Bloch decay or Hahn echo (γB1 / 2π = 62.5 kHz) pulse sequences and acquired by MAS at a rotation frequency of 14 kHz. Bloch pulse experiments achieved either π / 4 (2 μs) or π / 2 (4 μs) excitation pulses, and the Hahn echo pulse was optimized for each sample. The recycle delay was determined by the inversion recovery method. 7 It was determined by measuring the Li nuclear spin lattice relaxation (T1) time, which ranged from 75 to 300 ms. 7 The Li NMR spectrum was referenced to 0 ppm using a 1 M LiCl solution as an external reference. The NMR spectrum was processed in Topspin using exponential line expansion at -5 Hz. The data were: 1 Attempts were also made using H decoupling, but the NMR linewidth was not presented, and within these materials... 1 H- 7 The samples were not visibly affected by Li heteronuclear dipole coupling. Samples were prepared either by immersion in an electrolyte or by negative polarization in a supercapacitor. Immersed samples were prepared by adding approximately 2 ml of LiPF6 / MeCN electrolyte to 25 mg of Ni3BHT in a glass vial and allowing it to stand overnight. Polarized Ni3BHT1 electrodes were prepared by pressurizing Ni3BHT1 powder as a pellet and polarizing it in a three-electrode cell. The fabricated cells were first allowed to stand overnight, then scanned over 20 cycles at 5 mV / s in the potential range of 0 to -1.7 V vs OCP, held at -1.7 V for 5 minutes, and then decomposed. Both the immersion and polarization procedures resulted in the adsorption of Li ions at various available sorption sites, thus enabling analysis of the local chemical environment using ssNMR techniques. Wet samples of Ni3BHT1 immersion powder and polarization electrodes were gently washed with MeCN solvent to remove excess electrolyte ions remaining as free species in the macropores, and then dried under vacuum.

[0165] X-ray absorption spectroscopy (XAS) experiments were performed at the Advanced Photon Source (APS) at Argonne National Laboratory, using the 10-BM beamline. All measurements were performed in transmission mode at the Ni K edge (8.333 keV) with fast scans ranging from 250 eV (below the edge) to 550 eV (above the edge), taking approximately 10 minutes per scan. The sample was pressurized in a stainless steel sample holder and placed in the sample cell. The cell was sealed and moved to the beamline for measurement. At the Ni K edge, Ni-S (CN=1, R=2.28 Å) scattering pairs were simulated. o 2 This was calibrated by fitting foil. This was found to be 0.75. The least squares method of the first shell in r space and isolated q space was applied to fit the magnitude and imaginary components, from 2.7 to 10 Å for each spectrum. -1 Over the range of k 3 Weighted Fourier transform data were used. Polarized Ni3BHT1 samples were prepared by using an untreated Ni3BHT1 pellet as the working electrode in a three-electrode cell. The electrode was first allowed to stand overnight, then scanned at 5 mV / s for 20 cycles in the potential range of 0 to -1.7 V versus OCP, held at -1.7 V for 5 minutes, and then decomposed. After decomposition, the working electrode was carefully collected, rinsed with MeCN, and dried.

[0166] X-ray photoelectron spectroscopy (XPS) was performed using a Thermo Scientific K-Alpha XPS system with a hemispherical analyzer. Spectra were obtained using a monochromatic aluminum source Al Kα (ED1, 486.6 eV) with a standard emission geometry, a beam spot size of 400 microns, and an analyzer energy resolution of 0.1 eV. Surface charge neutralization was performed using a low-energy flood gun. The spectrum showed a charge referenced by an incidental C 1s, CC peak (at 284.8 eV). Polarized samples for ex situ analysis were prepared in the same manner as XAS samples. [Table 1] [Table 2]

[0167] X-ray diffraction pattern under polarization The PXRD patterns of untreated Ni3BHT1 and negatively polarized electrodes showed similar patterns with no apparent changes in peak position (Figure 37), Li + After ion intercalation, the interlayer packing distance shows a minimal change. This data indicates that the electrolyte Li during intercalation depends on the nature of the solvent-electrode surface interaction. + This suggests that ions may undergo partial or complete desolvation.

[0168] Ni3HITP2 as a control material for NMR 7 Li NMR studies were performed on samples immersed or negatively polarized in 1M LiPF6 electrolyte. Both immersion and polarization procedures resulted in the adsorption of Li ions at various available sorption sites, thus allowing for the analysis of local chemical environments using NMR techniques. Wet samples were gently washed with acetonitrile to remove excess electrolyte ions remaining as free species, and then dried under vacuum. NMR studies of Ni3BHT1 revealed the presence of two distinctly different chemical environments with respect to adsorbed Li ions, suggesting the possibility of ion sorption by intercalation between 2D sheets. To further understand this additional signal from Ni3BHT1, Ni3HITP2 was studied as a control material. Both Ni3HITP2 and Ni3BHT1 have a 2D structure with Ni as the metal node and also possess conductivity values ​​within two orders of magnitude.

[0169] While several embodiments of the present invention have been described and illustrated herein, those skilled in the art will readily imagine a variety of other means and / or structures for performing the functions described herein and / or obtaining one or more of the results and / or benefits, and each of such variations and / or modifications will be considered within the scope of the present invention. More generally, those skilled in the art will readily understand that all parameters, dimensions, materials and configurations described herein are illustrative, and that the actual parameters, dimensions, materials and / or configurations will depend on one or more specific applications in which the teachings of the present invention are used. Those skilled in the art can understand or verify many equivalents of the specific embodiments of the present invention described herein by means of ordinary experimentation alone. Therefore, it should be understood that the embodiments described herein are presented merely as examples, and that the present invention may be carried out in ways other than those specifically described and claimed, within the scope of the appended claims and their equivalents. The present invention covers each of the individual features, systems, articles, materials and / or methods described herein. Furthermore, any combination of two or more such features, systems, articles, and / or methods is included within the scope of the present invention, provided that such features, systems, articles, materials, and / or methods are not mutually inconsistent.

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

[0171] When the phrase "and / or" is used herein in and in claims, it should be understood that it means "either or both" of the elements thus linked, i.e., elements that exist in some cases conjugated and in other cases separately. Other elements may exist as needed, whether relating to or not relating to those elements specifically identified by the "and / or" phrase, unless otherwise explicitly stated. Thus, as a non-restrictive example, when used in conjunction with non-restrictive language such as "comprising," the expression "A and / or B" may refer to, in one embodiment, A without B (including elements other than B as needed); in another embodiment, B without A (including elements other than A as needed); and in yet another embodiment, 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 separating items in a list, “or” or “and / or” shall be interpreted as inclusive, that is, including at least one of several elements or lists of elements, but also including more than one, and additional unlisted items as appropriate. Only terms that explicitly express the opposite, such as “just one of” or “exactly one of” or, as used in the claims, “consisting of,” refer to including exactly one element of several elements or lists of elements. In general, where used herein, the term “or” shall be interpreted as simply indicating an exclusive alternative (i.e., “one or the other, but not both”) when preceded by an exclusive term such as “either,” “one of,” “just one of,” or “exactly one of.” Where used in the claims, “consisting of” shall have its usual meaning as used in the field of patent law.

[0173] Where used herein and in claims, the phrase “at least one” means, in reference to a list of one or more elements, at least one element selected from any one or more of the elements in the list of elements, but not necessarily requiring at least one of each and all of the elements specifically enumerated in the list of elements, and not excluding any combination of elements in the list of elements. This definition also allows elements to present, as needed, other than the elements specifically identified in the list of elements to which the phrase “at least one” refers, whether related to or unrelated to such elements. Therefore, as a non-restrictive example, “at least one of A and B” (or equivalently, “at least one A or B” or equivalently, “at least one A and / or B”) could mean, in one embodiment, at least one A including more than one as may be, and no B (and optionally including elements other than B); in another embodiment, at least one B including more than one as may be, and no A (and optionally including elements other than A); and in yet another embodiment, at least one A including more than one as may be, and at least one B including more than one as may be (and optionally including other elements).

[0174] In the claims and the above specification, all transitional phrases, including “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” and similar phrases, should be understood to be non-restrictive, meaning they include them but are not limited to them. Only the transitional phrases “consisting of” and “essentially consisting of” are considered closed or semi-closed transitional phrases, respectively, as described in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.

Claims

1. A metal-organic structure for use as a supercapacitor electrode material, wherein the metal-organic structure comprises a plurality of metal ions coordinated to a plurality of ligands, The aforementioned metal ions include nickel ions, cobalt ions, iron ions, platinum ions, and / or palladium ions. The plurality of ligands include ligands containing two or more sulfur donor atoms, The metal ion is coordinated to the ligand containing the two or more sulfur donor atoms by the two or more sulfur donor atoms, The aforementioned metal-organic structure has the following structure: 【Chemistry 1】 It has the following characteristics, where M is a metal ion: The metal-organic structure comprises a plurality of two-dimensional sheets having an average spacing greater than or equal to 0.3 nm and less than or equal to 0.5 nm. The metal-organic structure includes a plurality of pores having an average pore diameter greater than or equal to 0.3 nm and less than or equal to 1 nm. Metal-organic structures.

2. The metal-organic structure according to claim 1, wherein M is a nickel ion.

3. The metal-organic structure according to claim 1 or 2, wherein the metal-organic structure has a two-dimensional structure.

4. The metal-organic structure according to any one of claims 1 to 3, wherein the interaction energy between the plurality of two-dimensional sheets is less than the bond strength within the plurality of two-dimensional sheets.

5. The metal-organic structure according to any one of claims 1 to 4, wherein the two-dimensional sheets are aligned with one another.

6. The metal-organic structure according to any one of claims 1 to 5, wherein the average spacing between the two-dimensional sheets is greater than or equal to 0.3 nm and less than or equal to 0.4 nm.

7. The metal-organic structure according to any one of claims 1 to 6, wherein the plurality of pores are positioned within the plurality of two-dimensional sheets.

8. The metal-organic structure according to any one of claims 1 to 7, wherein the redox potential for the plurality of metal ions is greater than or equal to -3.0 V and less than or equal to -2 V, compared to a standard hydrogen electrode.

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