Electrochemical reduction of halogenated compounds containing sulfur pentahalide groups.

Abstract

Systems, products, and methods directed to electrochemical systems (e.g., batteries) and the electrochemical reduction of halogenated compounds are generally described. In certain embodiments, the halogenated compounds include at least one sulfur pentahalide (e.g., pentafluoride) group linked to a conjugated system. The subject matter of the present invention includes, in some cases, interrelated products, alternative solutions to a particular problem, and / or a number of different uses of one or more systems and / or products.

Description

[Technical field]

[0001] Related Applications This application claims priority to U.S. patent application Ser. No. 17 / 679,031, filed Feb. 23, 2022, and entitled "ELECTROCHEMICAL REDUCTION OF HALOGENATED COMPOUNDS COMPRISING A SULFUR PENTAHALIDE GROUP," the entirety of which is incorporated herein by reference for all purposes.

[0002] government support This invention was made with Government support under Grant No. W911NF-19-1-0311 awarded by the Army Research Office (ARO). The United States Government has certain rights in this invention.

[0003] Technical Field Systems, products, and methods directed to electrochemical systems (e.g., batteries) and the electrochemical reduction of halogenated compounds are generally described. In certain embodiments, the halogenated compounds include at least one sulfur pentahalide (e.g., pentafluoride) group bonded to a conjugated system. [Background technology]

[0004] background High energy density primary batteries are in high demand for long duration stand-alone systems such as unmanned vehicles, space applications, and implantable / portable medical devices. Due to the light weight of lithium (Li) and its low electrochemical potential, Li anodes allow the construction of batteries with high gravimetric and volumetric energy densities. Li primary batteries, for example, have 1470, 2180, and 1005 Wh / kg, respectively. 反応物 Li-SOCl2, Li-carbon monofluoride (Li-CF x), and Li-MnO2 systems are gaining market share. However, accidental voltage reversal in such Li-containing batteries can result in a thermal runaway condition, e.g., cell explosion or overheating. In addition, state-of-the-art Li-SOCl2 batteries utilize liquid SOCl2, which is highly toxic if exploded or leaked, and thus such batteries are not suitable for civilian applications where frequent handling and safe transportation or storage are essential. On the other hand, Li-CF x Although the batteries have improved safety, they face challenges such as poor high-rate performance and voltage delay on first discharge, and are therefore only suitable for low- to medium-rate applications. Improved systems, products, and methods for primary batteries are therefore desirable. Summary of the Invention [Means for solving the problem]

[0005] overview Systems, products, and methods directed to electrochemical systems (e.g., batteries) and the electrochemical reduction of halogenated compounds are generally described. In certain embodiments, the halogenated compounds include at least one sulfur pentahalide (e.g., pentafluoride) group linked to a conjugated system. The subject matter of the present invention includes, in some cases, interrelated products, alternative solutions to a particular problem, and / or a number of different uses of one or more systems and / or products.

[0006] According to certain embodiments, an electrochemical cell is described that includes a first electrode comprising an alkali metal and / or an alkaline earth metal, a second electrode, and a halogenated compound comprising at least one sulfur pentafluoride group bonded to a conjugated system.

[0007] In certain embodiments, an electrochemical cell includes a first solid electrode comprising an alkali metal and / or an alkaline earth metal, a second solid electrode comprising carbon monofluoride, and a liquid electrolyte, the liquid electrolyte comprising a halogenated compound, the halogenated compound comprising a sulfur pentafluoride group bonded to a conjugated system.

[0008] According to some embodiments, a method of reducing a halogenated compound is described, the method comprising discharging an electrochemical cell, the electrochemical cell comprising an alkali metal and / or alkaline earth metal and a halogenated compound. In certain embodiments, the discharging comprises oxidizing at least a portion of the alkali metal and / or alkaline earth metal and reducing at least a portion of the halogenated compound such that the halogenated compound is reduced by more than six electrons.

[0009] In certain embodiments, a method of reducing a halogenated compound includes providing a system including a first electrode comprising an alkali metal and / or an alkaline earth metal, a second electrode, and a halogenated compound, the halogenated compound comprising at least one sulfur pentafluoride group bonded to a conjugated system. In some embodiments, the method includes discharging the system, the discharging step including oxidizing at least a portion of the alkali metal and reducing at least a portion of the halogenated compound.

[0010] According to some embodiments, an electrochemical cell includes a first electrode comprising an alkali metal and / or alkaline earth metal, a second electrode, and a halogenated compound comprising at least one sulfur pentafluoride group bonded to a conjugated system, the specific energy of the electrochemical cell being greater than or equal to 2200 Wh / kg. 反応物 Equal to or higher than 2800Wh / kg 反応物 and the reactant is a halogenated compound.

[0011] According to one particular embodiment, the electrochemical cell comprises a first electrode comprising an alkali metal and / or alkaline earth metal, a second electrode, and a halogenated compound comprising at least one sulfur pentafluoride group bonded to a conjugated system, the total capacity of the electrochemical cell being 1000 mAh / g or more. 反応物 Equal to or greater than 1400mAh / g 反応物 and the reactant is a halogenated compound.

[0012] In certain embodiments, the electrochemical cell includes a first electrode comprising an alkali metal and / or an alkaline earth metal, a second electrode, and a halogenated compound comprising at least one sulfur pentafluoride group bonded to a conjugated system, the halogenated compound being: [ka] is selected from the group consisting of:

[0013] In some embodiments, the electrochemical cell includes a first electrode comprising an alkali metal and / or an alkaline earth metal, a second electrode, and a halogenated compound comprising more than one sulfur pentafluoride group bonded to a conjugated system.

[0014] In certain embodiments, an electrochemical cell includes a first electrode comprising an alkali metal and / or alkaline earth metal, a second electrode, and an electrolyte solution, the electrolyte solution comprising a halogenated compound at a concentration greater than or equal to 0.1 mM and less than or equal to 50 mM at 25° C. and 1 atm, the halogenated compound comprising at least one sulfur pentafluoride group bonded to a conjugated system.

[0015] In some embodiments, an electrochemical cell includes a first electrode comprising an alkali metal and / or an alkaline earth metal, a second electrode, and a liquid electrolyte, the liquid electrolyte being a halogenated compound comprising at least one sulfur pentafluoride group bonded to a conjugated system.

[0016] Other advantages and novel features of the present invention will become apparent from the following detailed description of various non-limiting embodiments of the present invention, taken in conjunction with the accompanying figures. In the event that the present specification and a document incorporated by reference include conflicting and / or inconsistent disclosure, the present specification shall control. In the event that two or more documents incorporated by reference include conflicting and / or inconsistent disclosure with respect to each other, the document having the later effective date shall control.

[0017] Non-limiting embodiments of the present invention are described by way of example with reference to the accompanying figures, which are schematic and are not intended to be drawn to scale. In the figures, each identical or nearly identical component shown is typically represented by a single number. For clarity, not every component in every figure is numbered, nor are every component of each embodiment of the present invention shown unless illustration is necessary for a person skilled in the art to understand the invention. [Brief description of the drawings]

[0018] [Figure 1A] FIG. 1A shows a schematic diagram of an electrochemical cell, according to some embodiments. [Figure 1B] FIG. 1B shows a schematic diagram of an electrochemical cell including alkali metal ions and / or alkaline earth metal ions, according to some embodiments. [Figure 1C] FIG. 1C shows a schematic diagram of an electrochemical cell including a reduced halogenated compound, according to some embodiments. [Figure 1D] FIG. 1D shows a schematic diagram of an electrochemical cell including a halogenated layer, according to some embodiments. [Diagram 2] FIG. 2 shows a non-limiting series of halogenated compounds according to some embodiments. [Diagram 3] FIG. 3 shows a non-limiting series of structures of RF-containing fluoroaromatics according to some embodiments. [Figure 4]FIG. 4 shows a general synthetic scheme for obtaining RF-containing fluoroaromatics, according to some embodiments. [Diagram 5] FIG. 5 shows a galvanostatic discharge profile of RF containing fluoroaromatics according to some embodiments. [Figure 6] 6A-6C show galvanostatic discharge profiles of a control group of fluorination reactants, according to some embodiments. [Figure 7] Figure 7A shows the galvanostatic discharge profile of a Lithium (Li) cell containing 0.1 M Ph-CN-C8(p), Figure 7B shows the galvanostatic discharge profile of a Li cell containing 0.1 M Ph-NO2-C6(o), and Figure 7C shows the galvanostatic discharge profile of a Li cell containing 0.1 M Ph-NO2-C8(o), according to some embodiments. [Figure 8] 8A and 8B show galvanostatic discharge profiles of a Li-cell containing 0.1 M Ph-NO2-C6(o) and 0.1 M Ph-NO2-C8(o), respectively, according to some embodiments. [Figure 9] 9A and 9B show powder X-ray diffraction (XRD) patterns of a fully discharged Ketjen Black (KB) electrode of a Li-Ph-NO2-C6(o) cell and a Li-Ph-CN-C8(p) cell, respectively, according to some embodiments. [Figure 10] 10A shows a scanning electron microscope (SEM) image of the KB electrode of a Li-Ph-CN-C8(p) cell fully discharged at 0.04 mA / cm2, according to some embodiments, FIG. 10B shows a SEM image of the KB electrode of a Li-Ph-CN-C8(p) cell fully discharged at 0.3 mA / cm2, according to some embodiments, and FIG. 10C shows a SEM image of the KB electrode of a Li-Ph-CN-C8(p) cell fully discharged at 0.5 mA / cm2, according to some embodiments. [Figure 11]FIG. 11 shows the galvanostatic discharge profile of a Li cell containing 0.1 M fluoroaromatic reactant including naphthalene functionalized with a fluoroalkane, according to some embodiments. [Figure 12] 12A and 12B show galvanostatic discharge profiles at room temperature (RT) and 50° C. of a Li-cell containing 0.1 M Ph-NO2-SF5(p), according to some embodiments. [Figure 13] 13A-13C show SEM images of a fully discharged Ph-NO2-SF5 cell according to some embodiments. [Figure 14A] FIG. 14A shows the galvanostatic discharge profile of a high concentration Ph-NO2-SF5 cell at 50° C. according to some embodiments. [Figure 14B] FIG. 14B shows the galvanostatic discharge profile at 50° C. of a 4M Ph-NO2-SF5 cell with a 15 mm diameter carbon cathode, according to some embodiments. [Figure 14C] FIG. 14C shows the galvanostatic discharge profile at RT of a 4M Ph-NO2-SF5 cell, according to some embodiments. [Figure 14D] FIG. 14D shows the galvanostatic discharge profile of a 4M Ph-NO2-SF5 cell at 50 °C, according to some embodiments. [Figure 15] FIG. 15 shows the achieved energy density of a Ph-NO2-SF5 cell in comparison to a CFx system, according to some embodiments. [Figure 16] FIG. 16 shows a Ragauni plot comparing the discharge performance at 50° C. of a Li-fluoroaromatic cell and a Li-CFx cell, according to some embodiments. [Figure 17A] FIG. 17A shows a synthetic scheme for compound Ph-H-C6, according to some embodiments. [Figure 17B] FIG. 17B shows a synthetic scheme for compound Py-C6, according to some embodiments. [Figure 17C]FIG. 17C shows a synthetic scheme for compound Ph-CN-C6(p), according to some embodiments. [Figure 17D] FIG. 17D shows a synthetic scheme for compound Ph-CN-C8(p), according to some embodiments. [Figure 17E] FIG. 17E shows a synthetic scheme for compound Ph-CN-C6(o), according to some embodiments. [Figure 17F] FIG. 17F shows a synthetic scheme for compound Ph-NO2-C6(o), according to some embodiments. [Figure 17G] FIG. 17G shows a synthetic scheme for compound Ph-NO2-C8(o), according to some embodiments. [Figure 17H] FIG. 17H shows a synthetic scheme for compound Ph-CF3-C6(o), according to some embodiments. [Figure 17I] FIG. 17I shows a synthetic scheme for compound Ph-CF3-C6(p), according to some embodiments. [Figure 17J] FIG. 17J shows a synthetic scheme for compound 1-Naph-C6, according to some embodiments. [Figure 17K] FIG. 17K shows a synthetic scheme for compound 2-Naph-C6, according to some embodiments. [Figure 18] FIG. 18 shows a non-limiting series of structures of halogenated compounds containing a sulfur pentafluoride group, according to some embodiments. [Figure 19] 19A and 19B show galvanostatic discharge profiles of the R-Ph-SF5 reactant, according to some embodiments, where the volume is normalized to the weight of the reactant, and the volume is normalized to the number of electron transfers per molecule, according to some embodiments. [Figure 20] Figure 20A shows a galvanostatic discharge profile of Br-Ph-2SF5, where the capacity is normalized to the weight of reactants, according to some embodiments, and Figure 20B shows a galvanostatic discharge profile of Br-Ph-2SF5, where the capacity is normalized to the number of electron transfers per molecule, according to some embodiments. [Figure 21A] FIG. 21A shows the discharge profile of NO2-Ph-SF5 under reactant-limited conditions with different cell termination voltages, according to some embodiments. [Figure 21B] FIG. 21B shows SEM images of the carbon cathode from a cell discharged to 2.38 or 1.90 V vs. Li / Li+, according to some embodiments. [Figure 21C] FIG. 21C shows a high-resolution F 1s X-ray photoelectron spectroscopy (XPS) spectrum of a discharged electrode, according to some embodiments. [Figure 21D] FIG. 21D shows an XPS survey spectrum (left) and the corresponding percentages of F, O, and S atoms (right), according to some embodiments. [Figure 21E] FIG. 21E shows the ultraviolet-visible (UV-vis) spectrum of the electrolyte extracted from the discharged cell as a function of termination voltage, according to some embodiments. [Figure 21F] FIG. 21F shows a corresponding photograph of the sample of FIG. 21E, according to some embodiments. [Figure 22A] FIG. 22A shows a mass spectrometry analysis of headspace gas from a fully discharged Li—NO 2 -Ph—SF 5 cell, according to some embodiments. [Figure 22B] FIG. 22B shows gas chromatography of headspace gas from a fully discharged Li-NO2-Ph-SF5 cell, according to some embodiments. [Figure 22C] FIG. 22C shows the galvanostatic discharge profile of a Li-NO2-Ph-SF5 cell and the corresponding cell pressure, according to some embodiments. [Figure 23A] FIG. 23A shows the galvanostatic discharge profile at 40 μA cm of a Li-NO2-Ph-SF5 cell as a function of NO2-Ph-SF5 concentration, according to some embodiments. [Figure 23B] FIG. 23B shows an SEM image of a carbon cathode with 3M NO2-Ph-SF5 / 0.2M LiClO4 / DMSO cathode / electrolyte fully discharged at 0.3 mA cm-2, according to some embodiments. [Figure 23C] FIG. 23C shows the theoretical and ultimate capacity and ultimate gravimetric energy of a Li-NO2-Ph-SF5 cell as a function of catholyte concentration, according to some embodiments. [Figure 23D] FIG. 23D shows the rate capability of a cell including 4M NO2-Ph-SF5 / 0.2M LiClO4 / DMSO, according to some embodiments. [Figure 24] FIG. 24 shows the ionic conductivity of NO2-Ph-SF5 containing electrolyte at 50° C. and RT as a function of NO2-Ph-SF5 concentration, according to some embodiments. [Diagram 25] FIG. 25 shows shelf life testing for a Li-NO2-Ph-SF5 cell with 4M NO2-Ph-SF5 / 0.2M LiClO4 / DMSO, according to some embodiments. [Figure 26A] FIG. 26A shows the weight breakdown of cell components for Li-CFx, Li-NO2-Ph-SF5, and hybrid cells, according to some embodiments. [Figure 26B] FIG. 26B shows a Ragauni plot comparing the rate performance of Li-CFx, Li-NO2-Ph-SF5, and hybrid cells, according to some embodiments. [Figure 26C] FIG. 26C shows the rate performance of a hybrid cell using CFx as a solid cathode and 4M NO2-Ph-SF5 / 0.2M LiClO4 / DMSO as a catholyte according to some embodiments. [Figure 26D] FIG. 26D shows SEM images of discharged cathodes of the Li-NO2-Ph-SF5 cell, the hybrid cell, and the Li-CFx cell, according to some embodiments. [Figure 27] FIG. 27 shows a theoretical capacity prediction of hybrid cells with various weight ratios, according to some embodiments. [Figure 28]FIG. 28 shows galvanostatic cycling profiles at 0.04 mA / cm (per cycle) of a Li-NO-Ph-SF cell with EC / DMC (left) and DMSO (right) catholyte solvents between 1.5 and 4.6 V and 1.9 and 3.9 V vs. Li / Li, respectively, according to some embodiments. [Figure 29] Figure 29A shows the galvanostatic discharge profile of a Na-NO2-Ph-SF5 cell containing 4M NO2-Ph-SF5 / 0.2M NaTFSI catholyte in DMSO and EC / PC according to some embodiments, and Figure 29B shows an SEM image of a discharged cathode substrate from the EC / PC-containing cell of Figure 29A according to some embodiments. [Diagram 30] FIG. 30 shows the galvanostatic cycling profile at 0.02 mA / cm between 1.2 and 4.5 V vs. Na / Na+ of a Na-NO2-Ph-SF5 cell with 0.1 M NO2-Ph-SF5 / 0.2 M NaTFSI in EC / DMC as the catholyte and KB as the cathode substrate according to some embodiments. [Diagram 31] FIG. 31 shows the galvanostatic discharge profile at 0.04 mA / cm and 50° C. of a Ca-NO2-Ph-SF5 cell including 4M NO2-Ph-SF5 / 0.2M CaTFSI in DMSO as the catholyte and carbon foam as the cathode substrate according to some embodiments. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] Detailed Description Systems, products, and methods directed to the electrochemical reduction of halogenated compounds are generally described. According to some embodiments, the electrochemical cells described herein include a first electrode comprising an alkali metal (e.g., Li) and / or an alkaline earth metal, a second electrode (e.g., comprising carbon), and a halogenated compound. In some embodiments, the halogenated compound includes a haloalkane (e.g., a fluoroalkane) linked to a conjugated system via at least one alkene or alkyne linker. In other embodiments, the halogenated compound includes a sulfur pentahalide (e.g., pentafluoride) group linked to a conjugated system that includes at least one substituted aromatic group. The halogenated compound may be dissolved in an electrolyte solvent and / or may be used in neat form as the electrolyte solvent itself. During discharge of the electrochemical cell, the high degree of conjugation of the halogenated compound facilitates electron transfer through the molecule, resulting in the complete (or near complete) dehalogenation of the molecule. In certain embodiments, the halogenated compound may be a halogenated compound, e.g., ... 13 Haloalkane functional group or -C8X 17 Halogenated compounds containing a haloalkane functional group can be reduced by 11 or 15 electrons, respectively, where X is a halogen, such as fluorine, chlorine, bromide, and / or iodide. Thus, the halogenated compound functions as a catholyte in some embodiments, and thus reduction of the halogenated compound provides an electrochemical cell (e.g., a battery) with increased energy and capacity compared to an otherwise equivalent electrochemical cell that does not include the halogenated compound.

[0020] Electrochemical cells including the halogenated compounds described herein offer significant advantages over conventional electrochemical systems. Conventional primary batteries that are commercially available, such as Li-SOCl2 and Li-CF xAlthough such batteries exhibit good electrochemical performance, they face various challenges. Li-SOCl2 primary batteries, for example, exhibit high cell-level energy densities (e.g., 480-590 Wh / kg or 950-1100 Wh / L), but utilize highly toxic and corrosive liquid SOCl2 as both the cathode and electrolyte, making such batteries unsuitable for civilian applications and / or transportation. Li-CF x Although the battery has a high theoretical specific energy (e.g., 2180 Wh / kg), CF x The particles are highly insulating and therefore Li-CF x The battery is only suitable for low to medium rate applications (e.g., 250-800 Wh / kg or 560-1160 Wh / L).

[0021] Li-fluorinated gas batteries, such as Li-SF6 and Li-NF3 batteries, can be used at RT in a single electrochemical cell setup for the defluorination of fluorinated compounds. The large degree of defluorination allows for the estimation of exceptionally high theoretical energy densities for gas reactants (e.g., 3900-5100 Wh / kg). 反応物 ). However, the limited kinetics and low solubility (e.g., less than 5 mM) achieved by the dissolved gas nature of SF6 and NF3 cathodes result in large overpotentials during cell discharge, thereby severely hindering the achievable energy density of these systems. Reduction of covalent C-F bonds can also be induced at high potentials (e.g., up to 3 V) in Li-perfluoroalkyliodide batteries. However, under practical cell operating conditions (with reactant concentrations equal to or greater than 1 M), cleavage of only one to two covalent C-F bonds per molecule can be achieved, thereby limiting cell-level energy density. Li-perfluorinated gas batteries and Li-perfluoroalkyliodide batteries are discussed in U.S. Patent Application Serial No. 16 / 909630, entitled "Electrochemical Formation of Substrate Coatings," which is incorporated herein by reference in its entirety.

[0022] The electrochemical cells described herein exhibit high energy density and capacity. 2 ), near complete dehalogenation of halogenated compounds can be achieved with between 8 and 15 e per molecule. - and a relatively high discharge potential (e.g., about 2.6 V). As a result, a high achievable specific energy (e.g., 2565 Wh / kg 反応物 up to 1140mAh / g 反応物 With increasing electrode potential (up to 1000 volts) now accessible, halogenated compounds become strong contenders for use as electrodes in high energy batteries (eg, primary batteries).

[0023] Furthermore, by adjusting the molecular structure of the halogenated compounds, a high degree of electrolyte solubility (e.g., equal to or less than 6M) is observed, thus reducing the overpotential resulting from low concentrations in existing metal-gas batteries, making the electrochemical cells described herein much more cost-effective than conventional systems, such as Li-CF x It becomes equivalent to a primary battery. In addition, the structure of halogenated compounds allows for multiple types of modifications (e.g., ring structure, type and position of substituents, haloalkene chain length, species of halogenated groups), and these modifications can directly affect the reduction of these molecules. This feature not only provides more opportunities for improving the electrochemical performance, but also serves as a new platform for investigating the reduction of halogen-containing molecules.

[0024] Turning to the figures, certain non-limiting embodiments are described in further detail. It should be understood that the present disclosure is not limited to the specific embodiments described herein, and that the various systems, components, features, and methods described with respect to these embodiments can be used either individually and / or in any desired combination.

[0025] FIG. 1A shows a schematic diagram of an electrochemical cell 10. According to certain embodiments, the electrochemical cell 10 includes a first electrode 12 (e.g., an anode). In some embodiments, the first electrode 12 is a metal 14 (M 0 where M is a neutral metal atom). In some embodiments, the metal has a standard reduction potential equal to or less than about -1.4 V versus the standard hydrogen electrode (SHE). For example, the metal may be an alkali metal and / or an alkaline earth metal in certain embodiments. Suitable examples of alkali metals include lithium (Li), sodium (Na), and / or potassium (K). Suitable examples of alkaline earth metals include magnesium (Mg) and / or calcium (Ca). In some non-limiting embodiments, for example, electrochemical cell 10 includes a first electrode 12 (e.g., anode) that includes a metal 14 that is Li. Other metals are possible.

[0026] In certain embodiments, the first electrode 12 (e.g., the anode) is or includes a metal 14 (e.g., an alkali metal). In some other embodiments, the metal 14 is another component of the electrochemical cell other than (or in addition to) the anode, or is present in another region of the electrochemical cell. For example, in certain embodiments, the metal may be suspended, dispersed, or dissolved in the electrolyte 26 (e.g., an electrolyte solution).

[0027] 1A, the electrochemical cell 10 can include a second electrode 16 (e.g., a cathode). As can be appreciated by one of ordinary skill in the art, the first electrode 12 and the second electrode 16 can be in ionic communication with each other, such that ions can move from the first electrode 12 to the second electrode 16 and vice versa. In some embodiments, the first electrode 12 and the second electrode 16 can be mechanically and / or electrically isolated from each other (e.g., by being placed in separate containers, using a separator, etc.).

[0028] The second electrode can include any of a variety of suitable materials. In certain embodiments, for example, the second electrode includes carbon and / or metal. In some embodiments, for example, the second electrode includes graphite, graphene, graphene oxide, carbon nanomaterials (e.g., carbon nanotubes, carbon nanofibers), carbon powder (e.g., Vulcan carbon, carbon black, etc.), and / or a carbon gas diffusion layer (GDL). In certain non-limiting embodiments, for example, the electrochemical cell 10 including the second electrode 16 (e.g., cathode) includes carbon (e.g., carbon black).

[0029] In certain embodiments, the second electrode comprises a carbonized material. As used herein, the term "carbonized material" generally refers to a carbon-containing composition that is heated under a controlled atmosphere that allows partial oxidation and the formation of extensive conjugation. The carbonized material may, in some embodiments, contain elements other than carbon, provided that elements other than carbon are present in the starting carbon-containing composition. In some embodiments, the carbonized material contains elements that enhance electrode performance. Non-limiting examples of non-carbon elements that the carbonized material may contain are metals (e.g., tin), nitrogen, phosphorus, oxygen, and / or silicon.

[0030] According to some embodiments, the second electrode is CF x As described in more detail herein, CF x The use of a cathode comprising: in combination with a halogenated compound in an electrochemical cell can provide enhanced electrochemical performance, for example increased specific energy.

[0031] The second electrode, in some embodiments, may include platinum (Pt), nickel (Ni), palladium (Pd), iron (Fe), cobalt (Co), gold (Au), and / or copper (Cu). According to certain embodiments, the second electrode may include a metal oxide (e.g., manganese oxide (MnO) or nickel oxide (NiO)), a metal sulfide, and / or a metal fluoride. Other materials are possible.

[0032] The various components of the electrochemical cell, including the anode active material, the cathode active material, the electrolyte, etc., are described in further detail herein.

[0033] Additionally, as described in more detail herein, the second electrode may include a halogenated layer.

[0034] The electrochemical cell can include the first electrode and / or the second electrode at any of a variety of suitable mass loadings. In some embodiments, for example, the electrochemical cell includes a first electrode and / or a second electrode at a loading of 0.1 mg / cm. 2 Equal to or greater than 1 mg / cm 2 Equal to or greater than 5 mg / cm 2 Equal to or greater than 10 mg / cm 2 Equal to or greater than 20 mg / cm 2 Equal to or greater than 30 mg / cm 2 Equal to or greater than 40 mg / cm 2 Equal to or greater than 50 mg / cm 2 Equal to or greater than 60 mg / cm 2 Equal to or greater than 70 mg / cm 2 Equal to or greater than 80 mg / cm 2 Equal to or greater than 90 mg / cm 2 Equal to or greater than 100 mg / cm 2 Equal to or greater than 120 mg / cm 2 Equal to or greater than 140 mg / cm 2 Equal to or greater than 160 mg / cm 2 Equal to or greater than 180 mg / cm 2 In certain embodiments, the electrochemical cell includes the first electrode and / or the second electrode with a mass loading of equal to or greater than 200 mg / cm.2 Equal to or less than 180 mg / cm 2 Equal to or less than 160 mg / cm 2 Equal to or less than 140 mg / cm 2 Equal to or less than 120 mg / cm 2 Equal to or less than 100 mg / cm 2 Equal to or less than 90 mg / cm 2 Equal to or less than 80 mg / cm 2 Equal to or less than 70 mg / cm 2 Equal to or less than 60 mg / cm 2 Equal to or less than 50 mg / cm 2 Equal to or less than 40 mg / cm 2 Equal to or less than 30 mg / cm 2 Equal to or less than 20 mg / cm 2 Equal to or less than 10 mg / cm 2 Equal to or less than 5 mg / cm 2 Equal to or less than 1 mg / cm 2 Combinations of the above recited ranges are also possible (e.g., the electrochemical cell may include a first electrode and / or a second electrode with a mass loading of less than or equal to 0.1 mg / cm 2 Equal to or greater than 200 mg / cm 2 The electrochemical cell may include a first electrode and / or a second electrode with a mass loading of less than or equal to 30 mg / cm 2 Equal to or greater than 70 mg / cm 2 (including mass loadings equal to or less than 1000 .mu.m). Other ranges are possible.

[0035] According to certain embodiments, the electrochemical cell includes a halogenated compound. As described herein, the term "halogenated compound" refers to an individual molecule of a halogenated compound. However, as can be understood by those skilled in the art, embodiments in which the electrochemical cell includes multiple halogenated compounds are also envisioned as the present disclosure is not meant to be limiting in this regard. With reference to FIG. 1A, for example, the electrochemical cell 10 includes a halogenated compound 11. The halogenated compound 11 in FIG. 1A is represented by the formula RX, where X represents at least one halogen (e.g., a fluorine ion) and R represents an organic group (e.g., at least one optionally substituted aliphatic group and at least one optionally substituted aromatic group) and / or an inorganic group (e.g., sulfur).

[0036] According to certain embodiments, the halogenated compound comprises a haloalkane. As used herein, the term "haloalkane" is given its ordinary meaning in the art and generally refers to a molecule comprising an alkane chain containing one or more halogens. In some embodiments, a haloalkane comprises a carbon-based backbone containing a carbon-halogen bond (e.g., a carbon-fluorine bond). The carbon backbone may be linear, cyclic, branched, and / or optionally substituted (e.g., with one or more different functional groups). In some non-limiting embodiments, a haloalkane comprises a C n X 2n+1 where n is equal to or greater than 1 and each X is the same or different halogen, such as fluorine, chlorine, bromine, and / or iodine. According to some embodiments, the haloalkane is of the form n X 2n+1 where n is equal to or greater than 1 and each X is the same (e.g., fluorine). According to certain non-limiting embodiments, for example, the haloalkane is of the form C6X 13 (For example, C6F 13 ) group or C8X 17 (For example, C8F 17) group. In certain other embodiments, the halogenated compound may comprise a mixture of haloalkanes. For example, in some embodiments, the halogenated compound comprises a mixture of fluoroalkanes, chloroalkanes, bromoalkanes, and / or iodoalkanes. The choice of haloalkane, in some embodiments, depends on several factors including cost, solubility, melting point, viscosity, stability prior to discharge of the electrochemical cell, and discharge efficiency.

[0037] In some embodiments, the haloalkane is bonded to a conjugated system. As used herein, the term "conjugated system" is given its usual meaning in the art and generally refers to a molecular system of p-orbitals with delocalized electrons, conventionally represented by alternating carbon single and multiple bonds. According to certain embodiments, the conjugated system comprises a continuous arrangement of at least four carbon atoms with π-orbital bonds between them. In some embodiments, the conjugated system may include a heteroatom, such as a nitrogen or oxygen atom, participating in a strong π bond with a carbon atom, instead of one or more of the carbon atoms. As can be generally understood by those skilled in the art, the π-orbitals in a conjugated system are delocalized, and the bonding interaction associated with one orbital is not limited to only between two carbons, as in the case of a localized bond, such as a C-C single bond or the carbon-carbon π bond of ethylene or acetylene.

[0038] In certain embodiments, the conjugated system comprises at least one aromatic group that is optionally substituted. As can be generally understood by those skilled in the art, aromatic groups have a cyclic structure that includes delocalized π bonds. In some embodiments, for example, the conjugated system comprises benzene. According to certain embodiments, the conjugated system can comprise more than one aromatic group that is optionally substituted (e.g., two aromatic groups that are optionally substituted, three aromatic groups that are optionally substituted, four aromatic groups that are optionally substituted, etc.). For example, in some embodiments, the conjugated system comprises naphthalene, anthracene, pyrene, and / or quinoline. As can be generally understood by those skilled in the art, when the conjugated system comprises more than one aromatic group that is optionally substituted, the aromatic stability on a per ring basis decreases, and the molecule reacts in a way that produces intermediates that maximize aromatic character, and as a result, the additional aromatic group that is optionally substituted behaves similarly to an alkene in terms of reactivity.

[0039] According to some embodiments, the haloalkane is linked to the conjugated system via at least one alkene or alkyne linker. In certain embodiments, the alkene linker may be of the form (e.g., -RC=CR-), and the alkyne linker may be of the form (e.g., -RC≡CR-), where R in each formula is the same or different and is hydrogen, an organic group (e.g., an optionally substituted aliphatic group, an optionally substituted aromatic group), and / or an inorganic group (e.g., nitrogen, oxygen, sulfur, etc.). The alkene or alkyne linker is part of the conjugated system in some embodiments, and thus the alkene or alkyne linker is present in the conjugation and participates in a delocalized bond with the conjugated system. For example, in some embodiments, the conjugated system may include at least one optionally substituted aromatic group (e.g., benzene) functionalized with an alkene or alkyne linker that results in a link to the haloalkane. In other embodiments, the conjugated system may include more than one optionally substituted aromatic group (e.g., naphthalene) functionalized with an alkene or alkyne linker that results in a link to a haloalkane. In yet other embodiments, the alkene or alkyne linker is part of one or more optionally substituted aromatic groups. For example, according to certain embodiments, the conjugated system may include more than one optionally substituted aromatic group, with the alkene or alkyne linker being bonded to one of the optionally substituted aromatic groups.

[0040] FIG. 2 shows a non-limiting series of halogenated compounds, each of which includes a haloalkane linked to a conjugated system via at least one alkene or alkyne linker, according to some embodiments. Structure A shows a conjugated system including benzene, an alkene linker as part of the conjugated system, and a haloalkane linked to the conjugated system via an alkene linker, according to certain embodiments. Structure B shows a conjugated system including benzene, an alkyne linker as part of the conjugated system, and a haloalkane linked to the conjugated system via an alkyne linker, according to certain embodiments. Structure C shows a conjugated system including naphthalene, two alkene linkers linked to the naphthalene as part of the conjugated system, and a haloalkane linked to the conjugated system via an alkene linker, according to certain embodiments. Structure D shows a conjugated system including anthracene, four alkene linkers linked to the anthracene as part of the conjugated system, and a haloalkane linked to the conjugated system via an alkene linker, according to certain embodiments. Structure E, according to certain embodiments, shows a conjugated system including quinoline, an alkene linker bonded to the quinoline as part of the conjugated system, and a haloalkane bonded to the conjugated system through the alkene linker. Structure F, according to certain embodiments, shows a conjugated system including quinoline, an alkyne linker bonded to the conjugated system, and a haloalkane bonded to the conjugated system through the alkyne linker. Structure G, according to certain embodiments, shows a conjugated system including naphthalene, an alkene linker bonded to the naphthalene as part of the conjugated system, and a haloalkane bonded to the conjugated system through the alkene linker. Structure H, according to certain embodiments, shows a conjugated system including anthracene, two alkene linkers bonded to the anthracene as part of the conjugated system, and a haloalkane bonded to the conjugated system through the alkene linker. It should be understood that the structures depicted in FIG. 2 are not meant to be limiting and that one of skill in the art can envision additional halogenated compounds that include a haloalkane linked to the conjugated system via at least one alkene or alkyne linker.

[0041] In certain non-limiting embodiments, the halogenated compound has the structure Ar-CH2=CH2-C n F 2n+1 wherein Ar contains at least one optionally substituted aromatic group, CH=CH is an alkene linker, and C n F 2n+1 is a fluoroalkane, and n is equal to or greater than 1. In certain embodiments, Ar contains one optionally substituted aromatic group (e.g., benzene, pyridine). In some embodiments, Ar contains more than one optionally substituted aromatic group (e.g., naphthalene).

[0042] According to some non-limiting embodiments, the halogenated compound is: [ka] [ka] is selected from the group consisting of:

[0043] As would be generally understood by one of ordinary skill in the art, other halogenated compounds comprising a haloalkane linked to the conjugated system via at least one alkene or alkyne linker are also possible as the present disclosure is not meant to be limiting in this regard.

[0044] According to certain embodiments, the halogenated compound comprises a sulfur pentahalide (e.g., pentafluoride) group bonded to the conjugated system. In some embodiments, the halogenated compound comprises at least one sulfur pentafluoride group bonded to the conjugated system. In certain embodiments, for example, the halogenated compound may comprise one sulfur pentafluoride group, two sulfur pentafluoride groups, three sulfur pentafluoride groups, four sulfur pentafluoride groups, or more than one sulfur pentafluoride group bonded to the conjugated system.

[0045] In some embodiments, the conjugated system may include a substituted aromatic group. In certain non-limiting embodiments, for example, the halogenated compound includes at least one sulfur pentafluoride group bonded to a conjugated system that includes a substituted benzene. Substitution of at least one sulfur pentafluoride group at the ortho, para, or meta position on the aromatic group advantageously results in the halogenated compound having increased solubility in the electrolyte, for example, compared to an equivalent halogenated compound that is otherwise unsubstituted on the benzene ring. The increased solubility of the halogenated compound contributes to an increase in the energy density associated with the electrochemical system during discharge.

[0046] In certain non-limiting embodiments, the halogenated compound is [ka] is selected from the group consisting of:

[0047] As would be generally understood by one of ordinary skill in the art, other halogenated compounds containing sulfur pentafluoride groups may also be envisioned as the present disclosure is not meant to be limiting in this regard, including halogenated compounds whose conjugated systems contain more than one aromatic group.

[0048] According to some embodiments, the halogenated compound may be ionic. In some embodiments, for example, the halogenated compound may include a charged (e.g., positively charged, negatively charged) ion. In certain embodiments, the charged ion is a heteroatom (e.g., a charged N atom, a charged O atom) in place of one or more carbon atoms of a conjugated system. In other embodiments, the charged ion may be a substituent of a conjugated system.

[0049] In some non-limiting embodiments, the halogenated compound is [ka] Includes.

[0050] As would be generally understood by one of ordinary skill in the art, other ionic halogenated compounds, including those containing sulfur pentafluoride groups, may also be envisioned as the present disclosure is not meant to be limiting in this regard.

[0051] In certain embodiments, a current and / or voltage is applied to the electrochemical cell. According to some embodiments, for example, the electrochemical cell can be charged and / or discharged.

[0052] In some embodiments, the electrochemical cell can be discharged to any of a variety of suitable capacities. In certain embodiments, for example, the discharge capacity can vary depending on the components of the electrochemical cell (e.g., the composition of the electrodes and / or electrolyte, etc.) and / or the amounts of the components of the electrochemical cell (e.g., the mass loading of the electrodes and / or electrolyte, etc.).

[0053] In some embodiments, the electrochemical cell has a capacity of 0.05 mAh / cm 2 Equal to or greater than 1mAh / cm 2 Equal to or greater than 2mAh / cm 2 Equal to or greater than 5mAh / cm 2 Equal to or greater than 10mAh / cm 2 Equal to or greater than 15mAh / cm 2 Equal to or greater than 20mAh / cm 2 Equal to or greater than 25mAh / cm 2 Equal to or greater than 30mAh / cm 2 Equal to or greater than 35mAh / cm 2 Equal to or greater than 40mAh / cm 2 Equal to or greater than 45mAh / cm 2 Equal to or greater than 50mAh / cm 2 Equal to or greater than 55mAh / cm 2In one particular embodiment, the electrochemical cell is discharged to a capacity (e.g., areal capacity) equal to or greater than 60 mAh / cm. 2 Equal to or less than 55mAh / cm 2 Equal to or less than 50mAh / cm 2 Equal to or less than 45mAh / cm 2 Equal to or less than 40mAh / cm 2 Equal to or less than 35mAh / cm 2 Equal to or less than 30mAh / cm 2 Equal to or less than 25mAh / cm 2 Equal to or less than 20mAh / cm 2 Equal to or less than 15mAh / cm 2 Equal to or less than 10mAh / cm 2 Equal to or less than 5mAh / cm 2 Equal to or less than 2mAh / cm 2 Equal to or less than 1mAh / cm 2 Combinations of the above noted ranges are also possible (e.g., the electrochemical cell is discharged to a capacity equal to or less than 0.05 mAh / cm 2 Equal to or greater than 60mAh / cm 2 The electrochemical cell is discharged to a capacity equal to or less than 10 mAh / cm 2 Equal to or greater than 15mAh / cm 2 (The areal capacity of an electrochemical cell is discharged to a capacity that is equal to or less than 10 ...

[0054] In certain embodiments, the electrochemical cell is fully discharged. As used herein, the term "fully discharged" generally means that the electrochemical cell is discharged until the theoretical capacity of the halogenated compound is reached, or until the theoretical capacity of the halogenated compound is not reached but the electrochemical cell stops due to cathode passivation (e.g., by LiF).

[0055] The electrochemical cell can be discharged at any of a variety of suitable current densities. In certain embodiments, the discharge capacity can vary depending on the particular components of the electrochemical cell (e.g., the composition of the electrodes and / or electrolyte) and / or the amounts of the components of the electrochemical cell (e.g., the mass loading of the electrodes and / or electrolyte, etc.).

[0056] According to some embodiments, the electrochemical cell has a current density of 1 microamp / cm 2 Equal to or greater than 500 microamperes / cm 2 Equal to or greater than 1 milliampere / cm 2 Equal to or greater than 2 milliamps / cm 2 Equal to or greater than 3 mA / cm 2 Equal to or greater than 4 mA / cm 2 Equal to or greater than 5 mA / cm 2 Equal to or greater than 6 mA / cm 2 Equal to or greater than 7 milliamps / cm 2 Equal to or greater than 8 milliamps / cm 2 Equal to or greater than 9 mA / cm 2 In some embodiments, the electrochemical cell is discharged at a current density equal to or greater than 10 milliamps / cm. 2 Equal to or less than 9 mA / cm 2 Equal to or less than 8 mA / cm 2Equal to or less than 7 mA / cm 2 Equal to or less than 6 mA / cm 2 Equal to or less than 5 mA / cm 2 Equal to or less than 4 mA / cm 2 Equal to or less than 3 mA / cm 2 Equal to or less than 2 milliamps / cm 2 Equal to or less than 1 milliamp / cm 2 Equal to or less than 500 microamperes / cm 2 Combinations of the above noted ranges are also possible (e.g., the electrochemical cell is discharged at a current density equal to or less than 1 microamp / cm 2 Equal to or greater than 10 milliamps / cm 2 The electrochemical cell is discharged at a current density equal to or less than 4 milliamps / cm 2 Equal to or greater than 6 mA / cm 2 (The discharge current is equal to or less than the current density of the charge carrier.) Other ranges are possible.

[0057] In some embodiments in which the second electrode comprises carbon, the electrochemical cell has a current of 50 mA / g C Equal to or greater than 500mA / g C Equal to or greater than 1A / g C Equal to or greater than 2A / g C Equal to or greater than 3A / g C Equal to or greater than 4A / g C Equal to or greater than 5A / g C Equal to or greater than 6A / g C Equal to or greater than 7A / g C Greater than 8A / g C Greater than 9A / g CIn certain embodiments, the electrochemical cell is discharged at a current density of 10 A / g or greater. C Equal to or less than 9A / g C Equal to or less than 8A / g C Equal to or less than 7A / g C Equal to or less than 6A / g C Equal to or less than 5A / g C Equal to or less than 4A / g C Equal to or less than 3A / g C Equal to or less than 2A / g C Equal to or less than 1A / g C Equal to or less than 500mA / g C Combinations of the above noted ranges are also possible (e.g., the electrochemical cell is discharged at a current density equal to or less than 50 mA / g C Equal to or greater than 10A / g C The electrochemical cell is discharged at a current density equal to or less than 1 A / g C Equal to or greater than 5A / g C (The discharge current is equal to or less than the current density of the charge carrier.) Other ranges are possible.

[0058] The electrochemical cell may be discharged (and / or charged) at any of a variety of suitable temperatures. In certain non-limiting embodiments, for example, the electrochemical cell is discharged (and / or charged) at a temperature above the freezing point of the electrolyte solvent. In some embodiments, the electrochemical cell is discharged (and / or charged) at a temperature equal to or greater than 10° C., equal to or greater than 20° C., equal to or greater than 30° C., equal to or greater than 40° C., equal to or greater than 50° C., equal to or greater than 60° C., equal to or greater than 70° C., or greater. In some embodiments, the electrochemical cell is discharged (and / or charged) at a temperature equal to or less than 80° C., equal to or less than 70° C., equal to or less than 60° C., equal to or less than 50° C., equal to or less than 40° C., equal to or less than 30° C., equal to or less than 20° C., equal to or less than 0° C., or less than 0° C. Combinations of the above-listed ranges are also possible (e.g., the electrochemical cell is discharged and / or charged at a temperature equal to or greater than 10° C. and equal to or less than 80° C., the electrochemical cell is discharged and / or charged at a temperature equal to or greater than 20° C. and equal to or less than 30° C.). Other ranges are also possible. In certain non-limiting embodiments, the electrochemical cell is discharged (and / or charged) at RT (e.g., between 20-22° C.).

[0059] According to certain embodiments, methods of discharging an electrochemical cell are described herein. In some embodiments, the discharging step includes oxidizing at least a portion of the alkali metal and / or alkaline earth metal, thereby providing alkali metal ions and / or alkaline earth metal ions. FIG. 1B shows a schematic diagram of an electrochemical cell including alkali metal ions and / or alkaline earth metal ions, according to some embodiments. As shown in FIG. 1B, the electrochemical cell 10 can be discharged (e.g., at any of a variety of suitable current densities), thereby providing electrons 8 from a first electrode 12 (e.g., an anode) including a metal 14 (e.g., an alkali metal and / or an alkaline earth metal). In some embodiments, discharging the electrochemical cell 10 results in the metal 14 being oxidized, thereby providing metal ions 18 (e.g., alkali metal ions). The metal ions 18 in FIG. 1B can be represented by the formula M + where M is a metal atom (e.g., a cationic alkali metal ion and / or a cationic alkaline earth metal ion) in an oxidized (e.g., +1, +2) oxidation state. In some embodiments, metal ions 18 are suspended, dispersed, and / or dissolved in electrolyte 26 (e.g., an electrolyte solution).

[0060] In certain embodiments, the discharging step includes reducing at least a portion of the halogenated compound, thereby providing a reduced halogenated compound. The reduced halogenated compound may include fragments in some embodiments. In certain embodiments, the reduced halogenated compound includes a charged species, a neutral species, or a radical. In some embodiments, reducing at least a portion of the halogenated compound may convert one or more atoms (e.g., one atom, two or more atoms, three or more atoms, etc.) of the halogenated compound from a first oxidation state to a second oxidation state. The oxidation number of the first oxidation state of the one or more atoms may be greater than the oxidation number of the second oxidation state. In some embodiments, the atom that is converted from the first oxidation state to the second oxidation state is a halogenated atom. As used herein, the term "halogenated atom" refers to an atom, such as a carbon atom or a sulfur atom, that is bonded (e.g., covalently, non-covalently) to one or more halogen atoms. Reduced halogenated compounds are described in more detail herein.

[0061] Halogenated compounds can be reduced by high electron number.As can be understood by those skilled in the art, the description of compounds (e.g., halogenated compounds) that can be reduced by electrons, as used herein, generally refers to the ability of the compound to obtain electrons in a reduction reaction as a result of redox electron transfer process.According to certain embodiments, halogenated compounds are reduced by 2 or more electrons, 4 or more electrons, 6 or more electrons, 8 or more electrons, 10 or more electrons, 11 or more electrons, 12 or more electrons, 14 or more electrons, 15 or more electrons, 16 or more electrons, 18 or more electrons, or more electrons. In some embodiments, the halogenated compound is reduced by less than or equal to 20 electrons, less than or equal to 18 electrons, less than or equal to 16 electrons, less than or equal to 15 electrons, less than or equal to 14 electrons, less than or equal to 12 electrons, less than or equal to 11 electrons, less than or equal to 10 electrons, less than or equal to 8 electrons, less than or equal to 6 electrons, less than or equal to 4 electrons, less than or equal to 2 electrons, or less than or equal to 2 electrons. Combinations of the above-mentioned ranges are also possible (e.g., the halogenated compound is reduced by less than or equal to 20 electrons, and the halogenated compound is reduced by less than or equal to 12 electrons). Other ranges are also possible.

[0062] In certain embodiments, the halogenated compound comprises a haloalkane bonded to the conjugated system through at least one alkene or alkyne linker, and the halogenated compound can be reduced by 6 or more electrons, 8 or more electrons, 10 or more electrons, 12 or more electrons, or 14 or more electrons. In some embodiments, the halogenated compound comprises a haloalkane bonded to the conjugated system through at least one alkene or alkyne linker, and the halogenated compound can be reduced by 16 or less electrons, 14 or less electrons, 12 or less electrons, 10 or less electrons, or 8 or less electrons. Combinations of the above listed ranges are also possible (e.g., the halogenated compound includes a haloalkane linked to the conjugated system via at least one alkene or alkyne linker, and the halogenated compound is capable of being reduced by greater than or equal to 6 and less than or equal to 14 electrons). Other ranges are also possible.

[0063] In certain embodiments, the halogenated compound comprises a sulfur pentafluoride group bonded to a conjugated system that includes at least one substituted aromatic group, and the halogenated compound can be reduced by two or more electrons, four or more electrons, six or more electrons, eight or more electrons, or ten or more electrons. In some embodiments, the halogenated compound comprises a sulfur pentafluoride group bonded to a conjugated system that includes at least one substituted aromatic group, and the halogenated compound can be reduced by less than twelve electrons, less than ten electrons, less than eight electrons, less than six electrons, or less than four electrons. Combinations of the above listed ranges are also possible (e.g., the halogenated compound includes a sulfur pentafluoride group linked to a conjugated system that includes at least one substituted aromatic group, and the halogenated compound is capable of being reduced by greater than or equal to 2 and less than or equal to 12 electrons). Other ranges are also possible.

[0064] The number of electrons to reduce a halogenated compound can be determined by techniques known to those of skill in the art. In some embodiments, for example, the number of electrons transferred (n e ) is the equation n e =Q / (m×F / 3.6), where Q is the reached capacity (mAh), m is the total number of moles of reactants, and F is the Faraday constant.

[0065] In certain non-limiting embodiments, for example, the halogenated compound comprises a haloalkane bonded to a conjugated system via at least one alkene or alkyne linker, where x is the number of halogen atoms on the haloalkane, and the halogenated compound is reduced by up to x-2 electrons. In other non-limiting embodiments, the halogenated compound comprises at least one sulfur pentafluoride group bonded to a conjugated system, where the number of fluorine atoms is x, the number of sulfur atoms is y, and the conjugated system is z. In some such embodiments, the halogenated compound can be reduced by up to x+2y+z electrons. In yet other non-limiting embodiments, the halogenated compound comprises at least one sulfur pentafluoride group bonded to a conjugated system and at least one substituent (e.g., NO2 group) bonded to a conjugated system, where the number of fluorine atoms is x, the number of sulfur atoms is y, the number of substituents is y', and the conjugated system is z. In some such embodiments, the halogenated compound can be reduced by up to x+2y+y'+z electrons.

[0066] In some embodiments, the conversion of a halogenated atom from a first oxidation state to a second oxidation state removes one or more halogen atoms (e.g., covalently bonded, non-covalently bonded) bonded to the halogenated atom (e.g., 2 or more halogen atoms, 4 or more halogen atoms, 6 or more halogen atoms, 8 or more halogen atoms, 10 or more halogen atoms, 12 or more halogen atoms, all halogen atoms). For example, the change in the oxidation state of one or more halogenated atoms can result in the scission of one or more halogenated atom-halogen bonds (e.g., 2 or more scission, 4 or more scission, 6 or more scission, 8 or more scission, 10 or more scission, 12 or more scission, all halogenated atom-halogen bonds). In certain embodiments, the change in oxidation state results in the conversion of the halogenated atom to a reduced non-halogenated atom. In some embodiments, scission of one or more halogenated atom-halogen bonds can result in the formation of one or more halide ions. In one non-limiting embodiment, for example, scission of one or more halogenated atom-halogen bonds can result in the formation of one or more fluorides (F), as described in more detail herein. - ) ions.

[0067] According to certain embodiments, the halogenated atom-halogen bond can be a carbon-halo (e.g., carbon-fluoro) bond. In some such embodiments, the discharging step comprises reducing equal to or more than 50% of the carbon-halo bonds of the halogenated compound, equal to or more than 60% of the carbon-halo bonds of the halogenated compound, equal to or more than 70% of the carbon-halo bonds of the halogenated compound, equal to or more than 80% of the carbon-halo bonds of the halogenated compound, equal to or more than 90% of the carbon-halo bonds of the halogenated compound, or more. In some embodiments, the discharging step includes reducing less than or equal to 100% of the carbon-halo bonds of the halogenated compound, less than or equal to 90% of the carbon-halo bonds of the halogenated compound, less than or equal to 80% of the carbon-halo bonds of the halogenated compound, less than or equal to 70% of the carbon-halo bonds of the halogenated compound, less than or equal to 60% of the carbon-halo bonds of the halogenated compound, or less than or equal to 60% of the carbon-halo bonds of the halogenated compound. Combinations of the above listed ranges are also possible (e.g., the discharging step includes reducing between less than or equal to 50% of the carbon-halo bonds of the halogenated compound and less than or equal to 100% of the carbon-halo bonds of the halogenated compound, the discharging step includes reducing between less than or equal to 70% of the carbon-halo bonds of the halogenated compound and less than or equal to 80% of the carbon-halo bonds of the halogenated compound).

[0068] According to certain embodiments, the halogenated atom-halogen bond can be a sulfur-halo (e.g., sulfur-fluoro) bond. In some such embodiments, the discharging step comprises reducing equal to or more than 50% of the sulfur-halo bonds of the halogenated compound, equal to or more than 60% of the sulfur-halo bonds of the halogenated compound, equal to or more than 70% of the sulfur-halo bonds of the halogenated compound, equal to or more than 80% of the sulfur-halo bonds of the halogenated compound, equal to or more than 90% of the sulfur-halo bonds of the halogenated compound, or more. In some embodiments, the discharging step includes reducing less than or equal to 100% of the sulfur-halo bonds of the halogenated compound, less than or equal to 90% of the sulfur-halo bonds of the halogenated compound, less than or equal to 80% of the sulfur-halo bonds of the halogenated compound, less than or equal to 70% of the sulfur-halo bonds of the halogenated compound, less than or equal to 60% of the sulfur-halo bonds of the halogenated compound, or less than or equal to 60% of the sulfur-halo bonds of the halogenated compound. Combinations of the above-listed ranges are also possible (e.g., the discharging step includes reducing between less than or equal to 50% of the sulfur-halo bonds of the halogenated compound and less than or equal to 100% of the sulfur-halo bonds of the halogenated compound, the discharging step includes reducing between less than or equal to 70% of the sulfur-halo bonds of the halogenated compound and less than or equal to 80% of the sulfur-halo bonds of the halogenated compound). Other ranges are also possible.

[0069] The incorporation of halogenated compounds into an electrochemical cell can advantageously provide a system with a higher specific energy than an otherwise equivalent electrochemical system that does not include the halogenated compounds. In some embodiments, for example, the specific energy of an electrochemical cell is greater than or equal to 600 Wh / kg. 反応物 Equal to or greater than 800Wh / kg 反応物 Equal to or greater than 1000Wh / kg 反応物 Equal to or greater than 1200Wh / kg反応物 Equal to or greater than 1400Wh / kg 反応物 Equal to or greater than 1600Wh / kg 反応物 Equal to or greater than 1800Wh / kg 反応物 Equal to or greater than 2000Wh / kg 反応物 Equal to or greater than 2200Wh / kg 反応物 Equal to or greater than 2400Wh / kg 反応物 Equal to or greater than 2600Wh / kg 反応物 Equal to or greater than 2800Wh / kg 反応物 and the reactant is a halogenated compound. In one particular embodiment, the specific energy of the electrochemical cell is equal to or greater than 3000 Wh / kg 反応物 Equal to or less than 2800Wh / kg 反応物 Equal to or less than 2600Wh / kg 反応物 Equal to or less than 2400Wh / kg 反応物 Equal to or less than 2200Wh / kg 反応物 Equal to or less than 2000Wh / kg 反応物 Equal to or less than 1800Wh / kg 反応物 Equal to or less than 1600Wh / kg 反応物 Equal to or less than 1400Wh / kg 反応物 Equal to or less than 1200Wh / kg 反応物 Equal to or less than 1000Wh / kg 反応物 Equal to or less than 800Wh / kg 反応物 and the reactant is a halogenated compound. Combinations of the above listed ranges are also possible (e.g., the specific energy of the electrochemical cell is less than or equal to 600 Wh / kg 反応物 Equal to or greater than 3000Wh / kg 反応物and the reactants are halogenated compounds. The specific energy of the electrochemical cell is 1800Wh / kg. 反応物 Equal to or greater than 2200Wh / kg 反応物 and the reactant is a halogenated compound). Other ranges are possible.

[0070] In certain embodiments, where the halogenated compound comprises a haloalkane linked to the conjugated system via at least one alkene or alkyne linker, the specific energy of the electrochemical cell is 600 Wh / kg. 反応物 Equal to or greater than 800Wh / kg 反応物 Equal to or greater than 1000Wh / kg 反応物 Equal to or greater than 1200Wh / kg 反応物 Equal to or greater than 1400Wh / kg 反応物 Equal to or greater than 1600Wh / kg 反応物 Equal to or greater than 1800Wh / kg 反応物 and the reactant is a halogenated compound. In some embodiments, the halogenated compound comprises a haloalkane linked to the conjugated system through at least one alkene or alkyne linker, the specific energy of the electrochemical cell is equal to or greater than 2000 Wh / kg. 反応物 Equal to or less than 1800Wh / kg 反応物 Equal to or less than 1600Wh / kg 反応物 Equal to or less than 1400Wh / kg 反応物 Equal to or less than 1200Wh / kg 反応物 Equal to or less than 1000Wh / kg 反応物 Equal to or less than 800Wh / kg 反応物and the reactant is a halogenated compound. Combinations of the above-listed ranges are also possible (e.g., the halogenated compound includes a haloalkane linked to the conjugated system via at least one alkene or alkyne linker, and the specific energy of the electrochemical cell is less than or equal to 600 Wh / kg 反応物 Equal to or greater than 2000Wh / kg 反応物 and the reactant is a halogenated compound). Other ranges are possible.

[0071] According to some embodiments in which the halogenated compound comprises a sulfur pentafluoride group linked to a conjugated system that includes at least one substituted aromatic group, the specific energy of the electrochemical cell is greater than or equal to 1000 Wh / kg. 反応物 Equal to or greater than 1200Wh / kg 反応物 Equal to or greater than 1400Wh / kg 反応物 Equal to or greater than 1600Wh / kg 反応物 Equal to or greater than 1800Wh / kg 反応物 Equal to or greater than 2000Wh / kg 反応物 Equal to or greater than 2200Wh / kg 反応物 Equal to or greater than 2400Wh / kg 反応物 Equal to or greater than 2600Wh / kg 反応物 and the reactant is a halogenated compound. In some embodiments, where the halogenated compound comprises a sulfur pentafluoride group linked to a conjugated system that includes at least one substituted aromatic group, the specific energy of the electrochemical cell is greater than or equal to 2800 Wh / kg 反応物 Equal to or less than 2600Wh / kg 反応物 Equal to or less than 2400Wh / kg 反応物 Equal to or less than 2200Wh / kg 反応物 Equal to or less than 2000Wh / kg 反応物Equal to or less than 1800Wh / kg 反応物 Equal to or less than 1600Wh / kg 反応物 Equal to or less than 1400Wh / kg 反応物 and the reactant is a halogenated compound. Combinations of the above-listed ranges are also possible (e.g., the halogenated compound includes a sulfur pentafluoride group linked to a conjugated system that includes at least one substituted aromatic group, and the specific energy of the electrochemical cell is less than or equal to 1000 Wh / kg). 反応物 Equal to or greater than 2800Wh / kg 反応物 and the reactant is a halogenated compound). Other ranges are possible.

[0072] In some embodiments, it may be particularly advantageous to utilize a solid-liquid hybrid electrochemical cell that includes a solid anode, a solid cathode, and a liquid electrolyte, where the liquid electrolyte includes a halogenated compound and the solid cathode includes a high capacity material that is voltage matched to the halogenated compound. In certain embodiments, for example, the solid cathode is CF x or MnO2. In some such embodiments, the achievable specific energy of the electrochemical cell may be relatively high. Without being bound by any theory, it is believed that the use of a large capacity voltage matched cathode (e.g., CF x or MnO2) and a halogenated compound may provide a relatively high specific energy compared to, for example, (i) an otherwise equivalent electrochemical cell that does not include a large capacity voltage-matched cathode or a halogenated compound, (ii) an otherwise equivalent electrochemical cell that does not include a large capacity voltage-matched cathode, or (iii) an otherwise equivalent electrochemical cell that does not include a halogenated compound.

[0073] According to certain embodiments, the incorporation of a halogenated compound into an electrochemical cell can advantageously provide a system with a greater total capacity than an otherwise equivalent electrochemical system that does not include the halogenated compound. In some embodiments, for example, the total capacity of the electrochemical cell is greater than or equal to 200 mAh / g. 反応物 Equal to or greater than 400mAh / g 反応物 Equal to or greater than 600mAh / g 反応物 Equal to or greater than 800mAh / g 反応物 Equal to or greater than 1000mAh / g 反応物 Equal to or greater than 1200mAh / g 反応物 and the reactant is a halogenated compound. In one particular embodiment, the total capacity of the electrochemical cell is 1400 mAh / g 反応物 Equal to or less than 1200mAh / g 反応物 Equal to or less than 1000mAh / g 反応物 Equal to or less than 800mAh / g 反応物 Equal to or less than 600mAh / g 反応物 Equal to or less than 400mAh / g 反応物 and the reactant is a halogenated compound. Combinations of the above listed ranges are also possible (e.g., the total capacity of the electrochemical cell is less than or equal to 200 mAh / g 反応物 Equal to or greater than 1400mAh / g 反応物 The total capacity of the electrochemical cell is equal to or less than 800 mAh / g 反応物 Equal to or greater than 1000mAh / g 反応物 (Equal to or less than 0.) Other ranges are possible.

[0074] In certain embodiments, where the halogenated compound comprises a haloalkane linked to the conjugated system via at least one alkene or alkyne linker, the total capacity of the electrochemical cell is greater than or equal to 200 mAh / g. 反応物Equal to or greater than 400mAh / g 反応物 Equal to or greater than 600mAh / g 反応物 Equal to or greater than 800mAh / g 反応物 Equal to or greater than 1000mAh / g 反応物 and the reactant is a halogenated compound. In some embodiments, the halogenated compound comprises a haloalkane linked to the conjugated system through at least one alkene or alkyne linker, the total capacity of the electrochemical cell is equal to or greater than 1200 mAh / g. 反応物 Equal to or less than 1000mAh / g 反応物 Equal to or less than 800mAh / g 反応物 Equal to or less than 600mAh / g 反応物 Equal to or less than 400mAh / g 反応物 and the reactant is a halogenated compound. Combinations of the above listed ranges are also possible (e.g., the halogenated compound includes a haloalkane linked to the conjugated system via at least one alkene or alkyne linker, and the total capacity of the electrochemical cell is less than or equal to 200 mAh / g. 反応物 Equal to or greater than 1200mAh / g 反応物 and the reactant is a halogenated compound). Other ranges are possible.

[0075] According to some embodiments in which the halogenated compound comprises a sulfur pentafluoride group linked to a conjugated system that includes at least one substituted aromatic group, the total capacity of the electrochemical cell is greater than or equal to 200 mAh / g. 反応物 Equal to or greater than 400mAh / g 反応物 Equal to or greater than 600mAh / g 反応物 Equal to or greater than 800mAh / g 反応物 Equal to or greater than 1000mAh / g 反応物Equal to or greater than 1200mAh / g 反応物 and the reactant is a halogenated compound. In some embodiments, where the halogenated compound comprises a sulfur pentafluoride group linked to a conjugated system that includes at least one substituted aromatic group, the total capacity of the electrochemical cell is 1400 mAh / g or more. 反応物 Equal to or less than 1200mAh / g 反応物 Equal to or less than 1000mAh / g 反応物 Equal to or less than 800mAh / g 反応物 Equal to or less than 600mAh / g 反応物 Equal to or less than 400mAh / g 反応物 and the reactant is a halogenated compound. Combinations of the above-listed ranges are also possible (e.g., the halogenated compound includes a sulfur pentafluoride group linked to a conjugated system that includes at least one substituted aromatic group, and the total capacity of the electrochemical cell is less than or equal to 200 mAh / g). 反応物 Equal to or greater than 1400mAh / g 反応物 and the reactant is a halogenated compound). Other ranges are possible.

[0076] FIG. 1C shows a schematic diagram of an electrochemical cell including a reduced halide compound, according to some embodiments. As shown in FIG. 1C and described herein, the electrochemical cell 10 can be discharged (e.g., at any of a variety of suitable current densities), thereby providing electrons 8 from a first electrode 12 (e.g., an anode). In certain embodiments, as a result of discharging the electrochemical cell 10, the halide compound 11 is reduced, thereby providing a reduced halide compound. In certain embodiments, the reduced halide compound can include one or more reduction products 22 (e.g., reduced non-halogenated atoms) and one or more halide ions 20. The reduction product 22 in FIG. 1C is represented by R′, where R′ represents a reduced organic group (e.g., at least one optionally substituted aliphatic group and / or at least one optionally substituted aromatic group) or a reduced inorganic group (e.g., sulfur). As described in more detail herein, R′ can be a charged species, a neutral species, or a radical. The halide ions 20 can be a halogen atom or a halogen atom, such as X - where X is a halide ion (e.g., anionic fluorine) in a reduced (e.g., −1) oxidation state. In certain embodiments, reduction product 22 and / or halide ion 20 resulting from the reduction of a halogenated compound may be dissolved in an electrolyte 26 (e.g., an electrolyte solution).

[0077] As described in further detail herein, in some embodiments, at least a portion of the alkali metal and / or alkaline earth metal is oxidized to provide alkali metal ions and / or alkaline earth metal ions, and at least a portion of the halide compound is reduced to provide a reduced halide compound (e.g., one or more reduction products and one or more halide ions). In certain embodiments, the method may further include reacting the alkali metal ions and / or alkaline earth metal ions with one or more halide ions to form a halide layer on at least a portion of the second electrode. The halide layer may include a metal salt (e.g., an alkali metal salt, an alkaline earth metal salt) in certain embodiments. In certain embodiments, the reaction product including the metal salt (e.g., an alkali metal salt, an alkaline earth metal salt) is deposited on a substrate (e.g., on the surface of the substrate) to form a halide layer. FIG. 1D shows a schematic diagram of an electrochemical cell including a halide layer, according to some embodiments. As shown in FIG. 1D, the second electrode 16 (e.g., the cathode) includes a halide layer 28 including a metal salt 24. 1D is represented by the formula MX, where M is a metal atom (e.g., an alkali metal ion, an alkaline earth metal ion) and X is a halide (e.g., a fluoride ion). In some non-limiting embodiments, for example, the second electrode 16 (e.g., the cathode) includes a halide layer 28 that includes the metal salt 24, which is LiF.

[0078] In some embodiments, the metal that reacts with the one or more halide ions may be selected such that the reaction between the metal and the one or more halide ions is exergonic. Without wishing to be bound by theory, it is believed that the exergonic reaction facilitates the electrochemical reaction and minimizes the presence of potentially dangerous reaction products and / or contaminants within the halide layer.

[0079] In certain embodiments, the reaction of alkali metal ions and / or alkaline earth metal ions with halide ions occurs at or near a charged interface of an electrochemical cell. As used herein, the term "charged interface" generally refers to an interface between two dissimilar materials where an interfacial potential difference exists. For example, in some embodiments, the charged interface can be an interface between a first material (e.g., an electrode) and a second material (e.g., an electrolyte) having a different composition than the first material. In some embodiments, the reaction of oxidized alkali metal ions with reduced halide compounds occurs at a charged interface between a substrate (e.g., a cathode) and an electrolyte (e.g., an electrolyte solution). For example, referring to FIG. 1D, the reaction of alkali metal ions and / or alkaline earth metal ions with halide ions can occur at a charged interface 29 between a second electrode 16 (e.g., a cathode) and an electrolyte 26 (e.g., an electrolyte solution). In some embodiments, as a result of the reaction between the oxidized alkali metal ions and the reduced halide compounds occurring at the charged interface 28 between the second electrode 16 (e.g., cathode) and the electrolyte 26, at least a portion of the reaction products including the metal salt 24 (e.g., alkali metal salt) deposit as a halide layer 28 on the second electrode 16 (e.g., cathode). In some embodiments, the reaction between the alkali metal ions and / or alkaline earth metal ions and the halide ions occurring at the charged interface 29 (e.g., between the second electrode 16 and the electrolyte 26) can provide a high concentration of the reaction products including the metal salt 24 at the charged interface 29. In certain embodiments, the charged interface 29 (e.g., between the second electrode 16 and the electrolyte 26) can be saturated and / or supersaturated with the reaction products including the metal salt 24 such that the metal salt 24 deposits as a halide layer 28 on the second electrode 16 (e.g., cathode).

[0080] The halogenation layer may, in certain embodiments, act as a passivation layer that protects the substrate on which it is disposed from degradation and / or decay that may be caused by external forces (e.g., the solvent and / or electrolyte of the electrochemical cell). In some embodiments, the halogenation layer is configured to protect at least a portion of the substrate (e.g., the electrode) from corrosion. Corrosion of the substrate (e.g., the electrode) may be caused in some cases by the electrochemical cell containing the substrate being cycled, thus resulting in subsequent reactivity between the substrate and the solvent and / or electrolyte of the electrochemical cell. Other external forces in the electrochemical cell, such as gases dissolved in the solvent of the electrochemical cell, may additionally cause corrosion of the substrate. In some embodiments, the halogenation layer may provide a reservoir of halide ions (e.g., fluoride ions).

[0081] The halogenated layer may include a plurality of particles having any of a variety of suitable average particle sizes. In some embodiments, for example, the plurality of particles has a characteristic average dimension (e.g., average particle size) that is equal to or greater than 1 nm and equal to or less than 500 nm. The average particle size of the plurality of particles may be determined using SEM, transmission electron microscope (TEM), and / or atomic force microscope (AFM).

[0082] According to certain embodiments, the average characteristic dimension of the plurality of particles may be inversely proportional to the discharge current density. For example, in some embodiments, higher current densities (e.g., 500 microamps / cm 2 ) discharge of the electrochemical cell at lower current densities (e.g., 40 microamperes / cm 2 ) may provide a plurality of particles having a smaller characteristic average size as compared to discharging an electrochemical cell.

[0083] The halogenated layer may have any of a variety of suitable average thicknesses. The thickness of the halogenated layer may be measured starting from the active surface of the second electrode, through the bulk of the halogenated layer, to the interface of the halogenated layer with the electrolyte. In some embodiments, the halogenated layer has an average thickness that is equal to or greater than 0.01 micrometers and equal to or less than 5 micrometers. The average thickness of the halogenated layer may be determined using XPS depth profiling, SEM, and / or TEM.

[0084] The halogenated layer can substantially cover the surface area of ​​the second electrode, in certain embodiments, for example, the halogenated layer covers between equal to or greater than 10% and equal to or less than 100% of the surface area of ​​the second electrode.

[0085] In some embodiments, at least a portion of the halogenated layer is polycrystalline and / or crystalline. For example, in certain embodiments, the halogenated layer may include nanocrystals. In certain embodiments, the crystalline (or polycrystalline) halogenated layer may include one or more crystallographic defects (e.g., point defects) and / or grain boundaries, and thus the halogenated layer may conduct ions (e.g., from the second electrode through the halogenated layer to the atmosphere surrounding the second electrode, e.g., the electrolyte). Methods for determining the crystallinity of the halogenated layer include, for example, TEM (e.g., electron diffraction in a TEM) and / or X-ray diffraction (XRD).

[0086] According to certain embodiments, at least a portion of the halogenated layer may be amorphous. In certain embodiments, it may be advantageous for at least a portion of the halogenated layer to be amorphous, since an amorphous halogenated layer may coat a larger surface area of ​​the second electrode compared to an otherwise equivalent halogenated layer that is crystalline and / or polycrystalline.

[0087] According to certain embodiments, the electrochemical cell may be a secondary battery (e.g., a rechargeable battery). In some such embodiments, the method may further include a step of charging the electrochemical cell. Charging the electrochemical cell electrochemically divides the alkali metal salt (e.g., LiF) in the halide layer, thus releasing the alkali metal ions (Li + ) and halide ions (e.g., F - ). In some embodiments, for example, alkali metal ions can be reduced back to alkali metals at the first electrode (e.g., anode), while halide ions are incorporated on and / or into the lattice of the second electrode (e.g., cathode). Thus, the halide layer acts as a reservoir for halide ions that will be incorporated on and / or into the second electrode of the electrochemical cell when the cell is cycled (e.g., charged and discharged). Second electrodes containing a halide layer and / or halide ions may be suitable for use in electrochemical cells, for example, primary and / or secondary batteries (e.g., Li cells and / or Li-ion cells), to provide lower charging potentials, increased capacity, and increased cyclability.

[0088] According to certain embodiments, as described herein, the electrochemical cell may include an electrolyte (e.g., an electrolyte solution). In some embodiments, the electrolyte is an electrolyte solution including, for example, an ionic salt dissolved in a solvent. The solvent may be water or an organic solvent in certain embodiments. For example, the electrolyte may include dimethylsulfoxide (DMSO), tetrahydrofuran (THF), dimethylformamide (DMF), dimethylacetamide, glyme, carbonate, and / or ionic liquid. Other solvents are possible. The electrolyte may include any of a variety of suitable ionic salts. For example, the electrolyte may include LiClO4, LiPF6, LiBF4, LiCF3SO3, LiNO3, LiI, LiBr, lithium bis(oxalato)borate, lithium bis(fluorosulfonyl)imide, and / or lithium bis(trifluoromethanesulfonyl)imide. Other ionic salts are also possible (e.g., Na derivatives of any of the aforementioned salts). In certain non-limiting embodiments, the electrolyte includes LiClO4 dissolved in DMSO. Further details regarding the function and composition of the electrolyte are described herein.

[0089] In some embodiments, the electrolyte comprises a halogenated compound. In certain embodiments, for example, the halogenated compound may be dissolved in any of the aforementioned solvents. According to some embodiments, the halogenated compound may have a relatively high concentration in the electrolyte solvent. In some such embodiments, the halogenated compound described herein may have a relatively high solubility in the electrolyte solvent. In some embodiments, for example, the solubility of the halogenated compound in the electrolyte is greater than or equal to 100 mM, greater than or equal to 500 mM, greater than or equal to 1 M, greater than or equal to 1.5 M, greater than or equal to 2 M, greater than or equal to 2.5 M, greater than or equal to 3 M, greater than or equal to 3.5 M, greater than or equal to 4 M, greater than or equal to 4.5 M, greater than or equal to 5 M, greater than or equal to 5.5 M, greater than or equal to 6 M, greater than or equal to 6.5 M, or greater at 25° C. and 1 atm pressure. In certain embodiments, the solubility of the halogenated compound in the electrolyte is less than or equal to 7M, less than or equal to 6.5M, less than or equal to 6.0M, less than or equal to 5.5M, less than or equal to 5M, less than or equal to 4.5M, less than or equal to 4M, less than or equal to 3.5M, less than or equal to 3M, less than or equal to 2.5M, less than or equal to 2M, less than or equal to 1.5M, less than or equal to 1M, less than or equal to 500 mM, or less, at 25° C. and 1 atm pressure. Combinations of the above recited ranges are also possible (e.g., the solubility of the halogenated compound in the electrolyte is between equal to or greater than 100 mM and equal to or less than 5 M at 25° C. and 1 atm, the solubility of the halogenated compound in the electrolyte is between equal to or greater than 1 M and equal to or less than 2 M at 25° C. and 1 atm). Other ranges are also possible.According to certain embodiments, the solubility of the halogenated compounds described herein in the electrolyte is higher than the solubility of halogenated gases (e.g., NF3 and / or SF6), thus advantageously providing the potential for electrochemical systems having relatively higher energy densities.

[0090] In other embodiments, the halogenated compound can be used as an additive, for example, in a relatively low concentration in an electrolyte solvent.In some such embodiments, for example, the solubility of the halogenated compound in the electrolyte when used as an additive is equal to or greater than 0.1 mM, equal to or greater than 0.5 mM, equal to or greater than 1 mM, equal to or greater than 5 mM, equal to or greater than 10 mM, equal to or greater than 20 mM, equal to or greater than 50 mM, equal to or greater than 100 mM, equal to or greater than 500 mM, or greater than that at 25° C. and 1 atm. In certain embodiments, the solubility of the halogenated compound in the electrolyte when used as an additive is less than or equal to 1M, less than or equal to 500mM, less than or equal to 100mM, less than or equal to 50mM, less than or equal to 20mM, less than or equal to 10mM, less than or equal to 5mM, less than or equal to 1mM, less than or equal to 0.5mM, or less than that at 25°C and 1atm. Combinations of the above listed ranges are also possible (e.g., the solubility of the halogenated compound in the electrolyte when used as an additive is between less than or equal to 1M and less than or equal to 5mM at 25°C and 1atm).

[0091] According to certain embodiments, the halogenated compound can be used in neat form, for example, as an electrolyte solvent in an electrochemical cell. In some such embodiments, an electrolyte salt (e.g., as described in more detail herein) can be dissolved in the halogenated compound.

[0092] As described herein, by reducing at least a portion of the halogenated compound, in some embodiments, a halide ion is provided. The halide ion can be fluoride, chloride, bromide, and / or iodide in certain embodiments. In certain embodiments, the halide ion (e.g., fluoride) is generated in a substantially anhydrous environment, for example, dissolved in an organic solvent of the electrolyte. In some embodiments, the fluoride (e.g., anhydrous fluoride) can be isolated and used as a reagent, for example, in a chemical reaction to produce one or more fluorinated compounds. Thus, in certain embodiments, the halogenated compounds described herein can be a source of soluble and / or anhydrous fluoride.

[0093] According to some embodiments, the electrochemical cell can be a non-rechargeable battery. In certain embodiments, for example, the battery is a primary battery that allows for safer and / or more complete utilization of alkali metals and / or alkaline earth metals compared to conventional primary batteries. In some embodiments, the battery (e.g., a primary battery) can be used in transportation (e.g., electric vehicles, unmanned vehicles), space applications, military applications, implantable / portable medical devices, and / or power grid and storage applications (e.g., power grids for storage of renewable energy).

[0094] According to certain embodiments, the electrochemical cell can be a rechargeable battery. In some embodiments, for example, the battery is a secondary battery that can be cycled (e.g., discharged and charged).

[0095] In certain embodiments, a system is described that includes a first electrode that includes an alkali metal and / or alkaline earth metal, a second electrode, and a halogenated compound that includes a haloalkane linked to a conjugated system via at least one alkene or alkyne linker. In some embodiments, the system is a water remediation system that can be used to reduce halogenated (e.g., fluorinated) compounds present in water, for example as contaminants.

[0096] The first electrode (e.g., anode) may include a variety of active materials (e.g., anode active materials). As used herein, the term "anode active material" refers to any electrochemically active species associated with the anode. In some embodiments, the anode active material is a metal. The metal may have a standard reduction potential of less than or equal to about -1.4V versus the standard hydrogen electrode (SHE). For example, the metal and / or anode may have a standard reduction potential of less than or equal to about -1.5V, less than or equal to about -1.6V, less than or equal to about -1.8V, less than or equal to about -2.0V, less than or equal to about -2.2V, less than or equal to about -2.4V, or less than or equal to about -2.5V versus the SHE. In some embodiments, the anode active material may include lithium, sodium, calcium, magnesium, aluminum, and / or combinations thereof. In some embodiments, the anode active material may include an alkali metal (e.g., lithium, sodium, potassium) and / or an alkaline earth metal (e.g., magnesium, calcium). In certain embodiments, the anode active material may include an alkali metal (e.g., lithium, sodium). In some embodiments, the anode may include an alkaline earth metal (e.g., magnesium, calcium).

[0097] In certain embodiments, the anode active material comprises Li. Suitable Li-containing anode active materials for use in the anode include, but are not limited to, lithium metal, such as lithium foils and lithium deposited on a substrate, lithium alloys (e.g., lithium-aluminum alloys and lithium-tin alloys), and / or lithium-containing three-dimensional materials, such as lithium wicked into high surface area carbon structures, including graphene or graphene oxide. These materials may be preferred in some embodiments, although other cell chemistries are contemplated. In some embodiments, the electrode may include one or more binder materials (e.g., polymers, etc.).

[0098] In some embodiments, the first electrode can have a thickness of less than or equal to 1500 micrometers, less than or equal to 1250 micrometers, less than or equal to 1000 micrometers, less than or equal to 750 micrometers, less than or equal to 500 micrometers, or less than or equal to 200 micrometers. In certain embodiments, the first electrode can have a thickness of at least 1 micrometer, at least 5 micrometers, at least 10 micrometers, at least 25 micrometers, at least 50 micrometers, at least 100 micrometers, or at least 150 micrometers. Combinations of the above-mentioned ranges are also possible (e.g., 1 micrometer to 1500 micrometers). Other ranges are also possible.

[0099] In some embodiments, the first electrode may include a passivation layer on at least a portion (e.g., substantially all) of one or more surfaces (e.g., two surfaces, all surfaces, surfaces in contact with the electrolyte). The passivation layer may, for example, prevent direct reaction of halogenated compounds with the first electrode (e.g., the metal of the first electrode). In some embodiments, the passivation layer may include organic compounds, oxides, halides, or combinations thereof, including but not limited to, alkali or metal oxides, carbonates, reduction products of the electrolyte, nitrides, fluorides, chlorides, or physical protective barriers, such as polymeric or conductive ceramics. The passivation layer may be formed in a separate chemical step, may be physically placed in the electrochemical cell, or may be chemically or electrochemically formed in situ in the electrochemical cell.

[0100] The second electrode (e.g., cathode) can include a variety of active materials (e.g., cathode active materials). As used herein, the term "cathode active material" refers to any electrochemically active species associated with the cathode. In some embodiments, the cathode active material includes carbon and / or one or more metals.

[0101] According to certain embodiments, the second electrode can have a thickness of less than or equal to 2000 micrometers, less than or equal to 1500 micrometers, less than or equal to 1250 micrometers, less than or equal to 1000 micrometers, less than or equal to 750 micrometers, less than or equal to 500 micrometers, or less than or equal to 200 micrometers. In certain embodiments, the second electrode can have a thickness of at least 1 micrometer, at least 5 micrometers, at least 10 micrometers, at least 25 micrometers, at least 50 micrometers, at least 100 micrometers, or at least 150 micrometers. Combinations of the above-mentioned ranges are also possible (e.g., 1 micrometer to 2000 micrometers). Other ranges are also possible.

[0102] In general, the second electrode can have any suitable surface area. Without wishing to be bound by theory, it is believed that the efficiency and extent of the electrochemical reaction increases with the surface area of ​​the second electrode (e.g., the cathode). In some embodiments, a second electrode having a relatively large surface area can be used. For example, the cathode can be about 10 m 2 / g or greater, approximately 250m 2 / g or greater, approximately 500m 2 / g or greater, approximately 750m 2 / g or greater, approximately 1000m 2 The surface area may be equal to or greater than 100 nm / g.

[0103] According to some embodiments, as described herein, the electrochemical cell includes an electrolyte. The electrolyte used in the electrochemical cell can function as a medium for the storage and transfer of ions, and in the special case of solid and gel electrolytes, these materials can function as a separator between the electrodes. Any liquid, solid, or gel material capable of storing and transferring ions can be used as long as the material facilitates the transfer of ions (e.g., Li ions) between the electrodes. The electrolyte is generally electronically non-conductive to prevent short circuits between the electrodes. The electrolyte can include one or more ionic electrolyte salts to provide ionic conductivity, and one or more liquid electrolyte solvents, gel polymer materials, or polymer materials. Suitable non-aqueous electrolytes can include organic electrolytes including one or more materials selected from the group consisting of liquid electrolytes, gel polymer electrolytes, and solid polymer electrolytes.

[0104] In some embodiments, the electrochemical cell includes a separator. The separator generally includes a polymeric material (e.g., a polymeric material that swells or does not swell upon exposure to an electrolyte). In some embodiments, the separator is located between the electrolyte and an electrode (e.g., a first electrode, a second electrode, an anode, a cathode). In certain embodiments, the separator is located between a first electrode (e.g., an anode) and a second electrode (e.g., a cathode). For example, referring to FIG. 1A, a separator 13 can be located between a first electrode 12 (e.g., an anode) and a second electrode 16 (e.g., a cathode). The separator can be configured to inhibit (e.g., prevent) physical contact between the first electrode and the second electrode, which can cause a short circuit of the electrochemical cell. The separator can be configured to be substantially electronically non-conductive, thereby inhibiting the extent to which the separator causes a short circuit of the electrochemical cell.

[0105] It will be understood that the above groups and / or compounds described herein may be optionally substituted with some substituents or functional moieties. That is, any of the above groups may be optionally substituted. As used herein, the term "substituted" is intended to include all permissible substituents of organic compounds, with "permissible" being within the context of the chemical rules of valency known to those skilled in the art. In general, the term "substituted", whether preceded by the term "optionally" or not, and the substituents contained in the formulas of the present invention, refers to the replacement of hydrogen radicals in a given structure with the radical of a particular substituent. When more than one position in any given structure can be substituted with more than one substituent selected from a particular group, the substituents can be the same or different at all positions. It will be understood that "substituted" also includes those substitutions that result in a stable compound that does not spontaneously undergo transformation, for example, by rearrangement, cyclization, elimination, etc. In some cases, "substituted" can generally refer to the replacement of hydrogen with a substituent as described herein. However, "substituted" as used herein does not encompass replacement and / or modification of functional groups critical to the identity of the molecule, such as when the "substituted" functional group becomes a different functional group through substitution. For example, a "substituted phenyl group" must still contain a phenyl moiety, and cannot be modified by substitution, for example, to become a pyridine ring, by this definition. In a broad aspect, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds. Exemplary substituents include, for example, those described herein. Permissible substituents may be one or more and may be the same or different for appropriate organic compounds. For purposes of this invention, heteroatoms, such as nitrogen, may have hydrogen substituents that fill the valence of the heteroatom, and / or any permissible substituent of organic compounds described herein. Furthermore, this invention is not intended to be limited in any manner by the permissible substituents of organic compounds.Combinations of substituents and variables envisioned by the present invention are preferably those that result in the formation of stable compounds useful in the formation of imaging agents or imaging agent precursors. The term "stable," as used herein, preferably refers to compounds that have sufficient stability to permit manufacture and maintain compound integrity for a sufficient period of time to be detected, preferably for a sufficient period of time to be useful for the purposes detailed herein.

[0106] Examples of substituents include halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amide, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamide, ketone, aldehyde, ester, heterocyclyl, aromatic or heteroaromatic moiety, -CF3, -CN, aryl, aryloxy, perhaloalkoxy, aralkoxy, heteroaryl, heteroaryloxy, heteroarylalkyl, heteroaralkoxy, azide, , amino, halide, alkylthio, oxo, acylalkyl, carboxyester, carboxamido, acyloxy, aminoalkyl, alkylaminoaryl, alkylaryl, alkylaminoalkyl, alkoxyaryl, arylamino, aralkylamino, alkylsulfonyl, carboxamidoalkylaryl, carboxamidoaryl, hydroxyalkyl, haloalkyl, alkylaminoalkylcarboxy, aminocarboxamidoalkyl, cyano, alkoxyalkyl, perhaloalkyl, arylalkyloxyalkyl, and the like.

[0107] The following examples are intended to illustrate certain embodiments of the present invention, but do not exemplify the full scope of the invention. EXAMPLES

[0108] Example 1 The following examples illustrate perfluorinated groups, such as perfluoroalkyl groups (R FBy defluorination of the fluorinated (SF5) and pentafluorosulfanyl (SF5) groups, a family of primary batteries capable of delivering large electrical energy is described.

[0109] A class of perfluorinated group-containing fluoroaromatics can achieve near complete defluorination under practical electrochemical cell operating conditions. F The structure of the aromatic compound is an aromatic group and a perfluoroalkane-containing group (R F ) and optimally an alkene group as the link between the former two moieties. For SF5-containing aromatics, the SF5 group is substituted directly on the aromatic, with no alkene group in between. The achievable specific energies of these reactants (e.g., R F 1785Wh / kg for aromatics 反応物 Up to 2190Wh / kg for NO2-Ph-SF5 反応物 and 2565Wh / kg for Br-Ph-2SF5 反応物 (up to 1000 keV) is higher than the theoretical value for SOCl2, making fluoroaromatics strong competitors for the cathode of high-energy Li primary batteries.

[0110] Non-limiting examples of fluoroaromatics are shown in FIG. n F 2n+1 The perfluoroalkane group is defined as a functional group (n is equal to or greater than 2) that promotes the reductive conversion of the perfluoroalkane group. As described in more detail herein, higher fluorine content results in higher energy density, and as a result, higher n values ​​may be advantageous. However, too long a perfluoroalkane chain may cause problems in the physical properties of the fluoroaromatics and the ability to achieve complete discharge of the electrochemical cell. As described in more detail herein, the non-limiting example shown in FIG. 3 is conveniently produced in one step and in high yield from commercially available starting materials.

[0111] A typical synthetic procedure to obtain fluoroaromatics is shown in Figure 4. A brief description of the synthesis is as follows. A mixture of aryl bromide (1.0 equiv.), perfluorinated alkene (1.5 equiv.), NaOAc (1.5 equiv.), n-Bu4NBr (0.85 equiv.), and palladium catalyst (0.050 equiv.) was dissolved in DMF and the reaction mixture was stirred at 125°C for 24-96 h or at 200°C for 1 h in a microwave reactor. Once the reaction mixture was cooled to RT, the residue was dissolved in AcOEt and HCl. The organic layer was separated, washed with water (x3) and brine, dried over MgSO4, and evaporated to dryness under reduced pressure. The residue was separated by chromatography on silica gel and the fractions containing the product were collected and evaporated to dryness.

[0112] Those skilled in the art will recognize that there are multiple methods for attaching perfluoroalkanes to compounds containing carbon-carbon double bonds, and many other structures can be produced other than the structure shown in FIG. 3 that may also be suitable materials for the products, systems, and methods described herein.

[0113] The fluoroaromatics shown in Figure 3 were generally obtained in good yields. For the synthesis of Py-C6, the use of Herrmann's catalyst as the palladium (Pd) catalyst did not result in any conversion, and therefore Pd(OAc)2 was utilized. Nevertheless, Py-C6 was only obtained in 31% yield, possibly due to the instability of the reaction intermediates or the coordination of pyridine to Pd resulting in complex by-products. For the synthesis of Ph-NO2-C6 and Ph-NO2-C8, the use of Pd(OAc)2 gave higher yields than the Herrmann catalyst. For Ph-NO2-C6(o) and Ph-CF3-C6(o), lower yields were observed than their para counterparts due to steric hindrance from the functional groups. In general, the C8 products were obtained in better yields due to the longer fluoroalkyl chains resulting in the products as solids with higher melting points and higher crystallinity.

[0114] First, R FIt was demonstrated how the reduction properties can be manipulated by molecular structure design. In certain cases where the electrolyte salt is insoluble in the neat reactant in liquid state, a co-solvent was used to aid in dissolving the electrolyte salt when the salt is insoluble in the neat reactant. Dimethyl sulfoxide (DMSO, no optimization) was chosen as the co-solvent for all cells tested. Due to the limited solubility of Ph-CN-C8(p) at RT, all cells were measured at 50°C with 0.1M reactant in DMSO electrolyte to form a fair comparison. The discharge performance was evaluated at 50°C and is shown in Figure 5, from which it can be analyzed how the molecular structure affects the discharge performance of these molecules.

[0115] R F To understand the effect of the chain length of the groups, the discharge profiles of Ph-NO2-C6(o) vs. Ph-NO2-C8(o) and Ph-CN-C6(p) vs. Ph-CN-C8(p) were compared. As shown in Figure 5, during the discharge of reactants containing C6 or C8, up to 11 e- or 15 e- transfers (calculated based on the capacity) can be obtained per molecule, respectively. Considering that the C6 or C8 group has only 13 or 17 C-F bonds, respectively, this discharge profile is in the range of 100 to 1500 e- transfers, assuming that all e- transfers are induced by the reduction of C-F bonds. F Near-complete defluorination of the R group could be achieved, indicating that only two C-F bonds remained unreacted. F It is also worth noting that chains that tend to exhibit better F utilization also tend to reduce the solubility of the reactants in DMSO. For example, Ph-CN-C6(p) is a liquid and miscible with DMSO at RT, whereas its C8 counterpart is a solid at RT and only becomes soluble at elevated temperatures (e.g., 50 °C).

[0116] Next, the effect of functional group type and their position was investigated using benzene as the basic ring structure. To compare between different functional groups, the Hammett's substituent constant σ, which is an index of the electron-withdrawing strength of the functional group, was considered. The σ of the investigated substituents (para) are shown in Table 1. [Table 1]

[0117] Since the Hammett rule does not give the best linear relationship with the ortho-substituent, we first investigated the reduction behavior change caused by different substituent positions (para vs. ortho) before other analyses. As shown in Figure 5, the discharge potential and capacity of Ph-CN-C6(o) and Ph-CN-C6(p) showed only slight differences, which indicates that the substituents at the para and ortho positions can affect the reduction of R F Based on this assumption, the discharge profiles of Ph-NO2-C6(o), Ph-CN-C6(o), and Ph-H-C6 were then compared, and it was concluded from the comparison that the stronger the electron-withdrawing effect of the substituent (σ = 0.78, 0.66, and 0 for -NO2, -CN, and -H, respectively) the higher the discharge potential of the reactant (2.6 V, 2.5 V, and 2.1 V, respectively).

[0118] Except for the electrochemical performance, the functional group type also directly affects the miscibility / solubility of the reactants in 0.1M LiClO4 / DMSO. Unlike Ph-CN-C8(p), which is insoluble at RT and has a limited solubility of 0.8M at 50°C, Ph-NO2-C8(o) can reach a concentration of 2M at RT. As for the trifluoromethyl group (-CF3), both Ph-CF3-C6(o) and Ph-CF3-C6(p) show only slight miscibility with 0.1M LiClO4 / DMSO even at 50°C, and thus the discharge performance of these reactants is not included.

[0119] In addition, the effect of different ring structures was investigated. By changing benzene to pyridine, i.e., from Ph-H-C6 to Py-C6, the discharge potential increased by about 0.1 V. This points out that even higher potentials (higher than 2.6 V for Ph-NO2-C6) can potentially be obtained by using pyridine as the basic ring structure with similar substituent modifications. However, this is outside the scope of the current study.

[0120] Finally, we demonstrate the necessity of including alkene and aromatic groups, and then the synthetic steps to build these functional groups throughout the molecule. In contrast to Ph-H-C6, R F The alkene group between the chain and the benzene is missing (i.e., perfluorohexylbenzene, R F When the aromatic group was absent, i.e., when the alkene group and R directly replaced the H on the benzene, little activity was observed during discharge (see FIG. 6A). F When only the R chain is present, the reactant is also electrochemically inactive (see FIG. 6B). In addition, when benzonitrile is added as an "external" aromatic group, the system (containing both aromatic and alkene groups, but not on the same molecule) still shows little activity (see FIG. 6C). This suggests that the synthetic process of putting these functional groups together as an entire molecule is a step in the synthesis of R F This indicates that the discharge profiles in Figures 6A-6C were evaluated at 50 °C.

[0121] Fluoroaromatics such as Ph-CN-C8(p), Ph-NO2-C6(o), and Ph-NO2-C8(o) show good rate capabilities during discharge. As shown in Figures 7A-7C, all three reactants exhibit a current density of 0.04 mA / cm at 50 °C. 2 to 1.0mA / cm 2 at such high rates as >1mAh / cm 2The attainable gravimetric capacities of Ph-CN-C8(p), Ph-NO2-C6(o), and Ph-NO2-C8(o) were 748, 642, and 681 mAh / g, respectively. 反応物 In terms of specific energy (normalized to the weight of only the active material, defined as Li + liquid reactant), the two C8 molecules have a specific energy that is 1600 Wh / kg for the C6 molecule (Ph-NO2-C6(o)). 反応物 ) than the slightly higher specific energies (1785 and 1700 Wh / kg for Ph-CN-C8(p) and Ph-NO2-C8(o), respectively). 反応物 In particular, these figures are approximately 1470Wh / kg 反応物 Although this is already higher than the theoretical specific energy of SOCl2, it is important to note that SOCl2-based batteries operate with neat SOCl2 (i.e., without an electrolyte diluent).

[0122] The rate performance at RT for Ph-NO2-C6(o) and Ph-NO2-C8(o) is shown in Figures 8A-8B. Both reactants showed slightly lower capacity compared to that obtained at 50 °C (at similar rates), but still good rate capacity persists at RT. The specific energy densities achievable at RT for Ph-NO2-C6(o) and Ph-NO2-C8(o) are 1470 and 1490 Wh / kg, respectively. 反応物 which are also comparable to the theoretical energy densities of SOCl2.

[0123] To demonstrate that the C-F bonds were indeed reduced during discharge, the solid discharge products formed on the carbon cathode were characterized. Note that a non-fluorinated salt (LiClO4) was used to avoid additional fluorine sources, and thus the only fluorine sources were the fluoroaromatics and the binder (polyvinylidene fluoride), the latter well known to be stable within the operating voltage window (1.9 V to 3.0 V). Hence, the formation of LiF directly indicates the C-F bond cleavage process for the fluoroaromatics.

[0124] As shown in Figures 9A-9B, LiF is the only crystallization product that can be detected from X-ray powder diffraction (XRD) after the discharge of Ph-CN-C8(p) and Ph-NO2-C6(o). In addition, the morphology of LiF particles formed from Ph-CN-C8(p) reduction was characterized using SEM. As shown in Figures 10A-10C, cubic LiF particles were formed on the carbon substrate and their size showed a significant dependence on the discharge rate. At a current density of 40 μA / cm 2 to 500μA / cm 2 For example, the average LiF particle size decreased from about 257±47 nm to about 93±17 nm, i.e., the LiF particle size decreased with increasing current density. It was concluded that C—F bond cleavage was indeed induced in the cell reduction reaction.

[0125] The discharge performance of fluoroaromatics containing more than one aromatic group was also investigated. Figure 11, for example, shows the discharge profile of a naphthalene molecule functionalized with a fluoroalkane. The discharge profile in Figure 11 was evaluated at 50°C.

[0126] R F Having demonstrated successful defluorination of the chain, we next investigated whether similar defluorination reactions could be induced for other perfluorinated groups, such as the SF5 group. F Note that aromatic containing compounds tend to exhibit the highest discharge potentials, so we investigated the discharge of Ph-NO2-SF5(p), a commercially available reactant in which nitro and SF5 groups replace two hydrogens at the para position on the benzene. As shown in Figures 12A-12B, the discharge of Ph-NO2-SF5(p) exhibits several distinct voltage plateaus at both temperatures tested (RT and 50 °C), with the discharge potential and reached capacity being slightly higher at the higher temperature. For Ph-NO2-SF5, the reachable gravimetric capacity and average voltage were 840 mAh / g at 50 °C. 反応物 and 2.6V, resulting in 2190Wh / kg 反応物 This results in a high energy density of R FAchievable energy density with aromatics (approx. 1700Wh / kg 反応物 ) to gain further insight into the stepwise reduction process. 2 The discharge profiles at 2000 and 50 °C were further analyzed (see FIG. 12B), and the low current was closest to equilibrium among the conditions examined. There are two main regions in the discharge curve. The first region has a flat voltage plateau at 2.9 V, contributing more than 60% of the total capacity, which is about 5 e per molecule. - The second region corresponds to approximately 3 e per molecule. - It has several different voltage steps with a capacity of 8 e - (calculated on a capacity basis). Since this multi-step profile is very similar to the multi-step profile of S reduction (polysulfides to LiS) observed in Li-S batteries, we hypothesized that the first plateau may be due to the cleavage of five SF bonds in the SF group, while the second part reflects sulfur reduction.

[0127] The morphology of LiF particles formed from the reduction of Ph-NO2-SF5 was characterized by SEM, see e.g., Figures 13A-13C.

[0128] The galvanostatic discharge profile of the high concentration (i.e., 3-4M) Ph-NO2-SF5 cell was also evaluated. Figure 14A shows the galvanostatic discharge profile of the high concentration Ph-NO2-SF5 cell at 0.3 mA / cm 2 The galvanostatic discharge performance at 50 °C and 3 M (as indicated) Ph-NO-SF in 0.1 M LiClO / DMSO as electrolyte, and 5 mg / cm 2 A carbon cathode substrate (diameter 12 mm) with a carbon loading of 0.3 mA / cm was used. Figure 14B shows the current density of the high-concentration Ph-NO2-SF5 cell at 0.3 mA / cm 2 The galvanostatic discharge performance at 50 °C and 4 M Ph-NO-SF in 0.1 M LiClO / DMSO as electrolyte and 5 mg / cm 2A carbon cathode substrate with a carbon loading of 1.0 μm was utilized. To obtain better gravimetric performance, a larger cathode substrate (15 mm diameter) was used, and thus the capacity units are mAh / cm. 2 Figure 14C shows the 0.1 mA / cm2 charge of the high-concentration Ph-NO2-SF5 cell. 2 The galvanostatic discharge performance at 1000 mA and RT is shown. The cell was constructed with 4 M Ph-NO-SF in 0.1 M LiClO / DMSO as the electrolyte and 5 mg / cm 2 A carbon cathode substrate (diameter 12 mm) with a carbon loading of 0.3 mA / cm was utilized. In addition, Figure 14D shows the current density of the high-concentration Ph-NO2-SF5 cell at 0.3 mA / cm 2 The galvanostatic discharge performance at 50 °C and 50 °C is shown. The cell was charged with 200 μL of 4 M Ph-NO-SF in 0.2 M LiClO / DMSO as the electrolyte and 5 mg / cm 2 A carbon cathode substrate (diameter 15 mm) with a carbon loading of 0.1 wt.

[0129] Figure 15 shows the CF x Figure 1 shows the achieved energy density of the Ph-NO2-SF5 cell compared to the system. The energy density was normalized to the weight of the active material, electrolyte, solvent, and carbon. CF x Data about purchased CF x Thin CF prepared using powder x Electrode (loading amount approx. 1mg / cm 2 ) was used for the measurements.

[0130] The Li-fluoroaromatic battery disclosed herein is a state-of-the-art Li-CF x Higher reactant concentrations (>2M) are required to achieve battery equivalence. If a 0.1M concentration is used, the DMSO would weigh 20 times more than the reactants, and therefore the energy density normalized to the weight of active materials and electrolyte would be lower. In contrast, R FReactant concentrations of 2M for aromatics containing and 4M for aromatics containing SF5 were assumed (hence DMSO / reactant = 0.4:1 w / w), resulting in similar discharge performance (11, 15, and 8 e per molecule for C6, C8, and SF5 reactants, respectively). - If the transfer of heat from the source to the source is still possible, the energy density is >1000Wh / kg. 活物質+電解質 (See FIG. 16). Note that these numbers for the high reactant concentrations were directly extrapolated from the numbers at the low concentrations.

[0131] To evaluate the potential of the disclosed system, its performance at high concentrations was compared with that of state-of-the-art Li-CF x Compared with Li-CF batteries. x The cell discharge performance was compared with the purchased CF x Measured at 50°C using powder (coating on Toray paper substrate). Excess electrolyte is required for laboratory scale cells, and electrolyte weight is typically 100% for commercial Li-CF x No battery information was reported, so for a fair comparison, we used the CF x Assuming a weight ratio of 1:1 between the electrolyte and the electrolyte, the resulting gravimetric energy density (CF x (by weight) electrolyte + CF x The electrolyte / CF x The weight ratio of CF x are typical values ​​reported for batteries and therefore commercially available CF x It is worth noting that this is a reasonable assumption to represent the cell. As shown in FIG. 16, at fluoroaromatic concentrations of 2M or 4M, the cell is R F Li-CF for aromatics containing (approx. 1100Wh / kg) and aromatics containing SF5 (approx. 1500Wh / kg) x It is expected to exhibit an energy density comparable to or better than that of a battery.

[0132] As described herein, Li-perfluorinated gas batteries, such as Li-SF6 and Li-NF3 systems, exhibit high theoretical energy density (3922 Wh / kg and 5072 Wh / kg for SF6 and NF3, respectively) and high chemical stability, and are therefore promising electrochemically active components for primary battery applications. However, gas molecules have low solubility in non-aqueous electrolytes and require an electrode adsorption process before the molecules can be successfully reduced, which is difficult for symmetric perfluorinated (i.e., inactive) reactants. Hence, large overvoltages were observed during discharge. A second practical consideration is that gas systems also require a gas headspace in an electrochemical cell setup, which can be an additional burden on cell-level energy density.

[0133] To address these issues, we developed a Li-perfluoroalkyl iodide battery that utilizes a fluorinated liquid as the cathode. F The chain-bearing, commercially available reactant is widely used as a building block in organic synthesis. Using this reactant as a model system, F We demonstrated that reduction of the chain at RT is achievable in a single-cell setup at high potentials (up to 3.0 V). However, near-complete defluorination of the reactants was not achieved. Therefore, further optimization is still required before the Li-perfluoroalkyl iodide battery is feasible for practical applications.

[0134] The systems described herein utilizing fluoroaromatics as the cathode exhibit the following advantages, including high energy density, improved rate capability, and more design flexibility.

[0135] With regard to high energy density, near complete defluorination of fluoroaromatics is possible under practical discharge conditions (e.g., 0.3 mA / cm 2 ) with 8 to 15 e per molecule. -This results in a relatively high discharge potential (about 2.6 V) and a high specific energy (e.g., 2190 Wh / kg for NO2-Ph-SF5). 反応物 Up to 100% solubility (up to 100% solubility) was observed, making fluoroaromatics strong competitors for the cathode of high-energy Li primary batteries. By adjusting the molecular structure, high solubilities (>2M) were reached (for Ph-NO2-C6(o) and Ph-NO2-C8(o)). Hence, Li-CF x It is reasonable to believe that cell-level energy densities comparable to or even higher than those of batteries can be achieved.

[0136] With regard to improved rate capacity, since the fluoroaromatics are in the liquid phase (dissolved in the electrolyte), the transport-related kinetics are similar to that of the CF x In addition, the disclosed system allows for high concentrations of reactants, thereby reducing the overpotential that arises from low concentrations in other existing metal-gas batteries.

[0137] For further design flexibility, the molecular structures of the aforementioned commercialized cathodes are relatively simple and difficult to modify and therefore difficult to improve cell performance, requiring focus on other cell components, such as electrolytes, supporting carbons, or catalysts. In contrast, fluoroaromatic molecules are amenable to multiple types of modifications (ring structures, types and positions of substituents, R F These modifications allow for a variety of functional groups (chain length, fluorinated group type, etc.) and these modifications can directly affect the reduction properties of these molecules. This not only provides more opportunities for improving the electrochemical performance but also serves as a new platform for investigating the reduction of fluoride bonds, thus bringing further scientific insights into chemical and electrochemical studies.

[0138] Furthermore, the role of π electrons and substituents in fluoroaromatics is very important to achieve complete reduction and therefore optimal energy density. This enhancement can be the result of increased charge transfer, potentially resulting in transient or persistent carbon-containing products that enhance charge transfer. Optimizing the interfacial interaction of fluoroaromatics with the anode is also very important, and fluorine materials can exhibit an effect also known as the fluorous effect, in which they become incompatible with other organic materials and are unable to optimally wet the interface with the electrode. For optimal charge injection, these interfaces can be modified with groups containing perfluoroalkanes or perfluoroaromatics. It has also been shown that different substituents attached to the aromatic ring can impart different discharge characteristics. In some embodiments, a mixture of different reducible fluoroaromatics results in the desired performance. This consideration includes long-term stability, power, and energy density.

[0139] The disclosed fluoroaromatic battery system exhibits high rate capacity and is comparable to state-of-the-art Li-CF x It has the potential to deliver high cell-level energy densities that are comparable to or even better than batteries, making this technology highly valuable for implantable devices (e.g., cardiac pacemakers), on-board power, remote human operation (e.g., space exploration), memory or emergency back-up, military applications, and other electronic devices. Example 2

[0140] The following examples are F The experimental methods and synthesis of aromatic containing compounds are described.

[0141] All chemical reagents were purchased from MilliporeSigma, Synquest Laboratories, Oakwood Chemicals, or TCI and used without purification unless otherwise indicated. Thin-layer chromatography was performed using Baker-flex Silica Gel 1B-F plates (JT Baker). Flash chromatography was performed using technical grade silica gel with 60 Å pores and 230-400 mesh particle size (Sigma-Aldrich, 717185).

[0142] 1 H, 13 C, and 19 F nuclear magnetic resonance (NMR) spectra were recorded on a JEOL model JNM-ECZ500R / S1 spectrometer operating at 500, 126, and 471 MHz, respectively. 1 H and 13 For C NMR spectra, deuterated solvent standards were used as internal standards ( 1 H: 7.26 ppm indicates CDCl3; 13 C: 77.16 ppm indicates CDCl3). Direct analysis in real time (DART) mass spectra were obtained at the MIT Department of Chemistry Instrumentation Facility.

[0143] Synthesis of compound Ph-H-C6 shown in Figure 17A: A mixture of bromobenzene (313 mg, 1.99 mmol), 1H,1H,2H-perfluoro-1-octene (1.04 g, 2.99 mmol), NaOAc (255 mg, 3.11 mmol), n-Bu4NBr (553 mg, 1.72 mmol), and Herrmann's catalyst (98 mg, 0.105 mmol) was dissolved in DMF (10 mL) and the reaction mixture was stirred at 200 °C for 1 h in a microwave reactor. Once the reaction mixture was cooled to RT, the residue was dissolved in AcOEt (50 mL) and 1M HCl (50 mL). The organic layer was separated, washed with water (50 mL x 3) and brine (50 mL), dried over MgSO4, and evaporated to dryness under reduced pressure. The residue was separated by chromatography on silica gel using hexane as eluent, and the fraction containing compound Ph-H-C6 (R f =0.50 in hexanes) was collected and evaporated to dryness to give a colorless oil (490 mg, 1.16 mmol, 58% yield).

[0144] Synthesis of compound Py-C6 shown in FIG. 17B: A mixture of 3-bromopyridine (316 mg, 2.00 mmol), 1H,1H,2H-perfluoro-1-octene (1.06 g, 3.06 mmol), NaOAc (254 mg, 3.10 mmol), n-Bu4NBr (548 mg, 1.70 mmol), and Pd(OAc)2 (23 mg, 0.102 mmol) was dissolved in DMF (10 mL) and the reaction mixture was stirred at 200° C. for 1 h in a microwave reactor. Once the reaction mixture was cooled to RT, the residue was dissolved in AcOEt (50 mL) and H2O (50 mL). The organic layer was separated, washed with water (50 mL×3) and brine (50 mL), dried over MgSO4, and evaporated to dryness under reduced pressure. The residue was separated by chromatography on silica gel using CH2Cl2 as eluent, and the fraction containing compound Py-C6 (R f =0.45 in CH2Cl2) was collected and evaporated to dryness to give a colorless oil (260 mg, 0.614 mmol, 31% yield).

[0145] Synthesis of compound Ph-CN-C6(p) shown in Figure 17C: A mixture of 4-bromobenzonitrile (362 mg, 1.99 mmol), 1H,1H,2H-perfluoro-1-octene (1.04 g, 3.00 mmol), NaOAc (246 mg, 3.00 mmol), n-Bu4NBr (540 mg, 1.68 mmol), and Herrmann's catalyst (75 mg, 0.080 mmol) was dissolved in DMF (10 mL) and the reaction mixture was stirred in a microwave reactor at 200 °C for 1 h. Once the reaction mixture was cooled to RT, the residue was dissolved in AcOEt (50 mL) and 1M HCl (50 mL). The organic layer was separated, washed with water (50 mL x 3) and brine (50 mL), dried over MgSO4, and evaporated to dryness under reduced pressure. The residue was separated by chromatography on silica gel using a gradient of 1% to 5% CH2Cl2 in hexane as eluent, and the fraction containing compound Ph-CN-C6(p) (R f = hexane, 0.35 in 33% CH2Cl2) was collected and evaporated to dryness to give a beige solid (380 mg, 0.850 mmol, 43% yield).

[0146] Synthesis of compound Ph-CN-C8(p) shown in Figure 17D: A mixture of 4-bromobenzonitrile (364 mg, 2.00 mmol), 1H,1H,2H-perfluoro-1-decene (1.34 g, 3.00 mmol), NaOAc (246 mg, 3.00 mmol), n-Bu4NBr (548 mg, 1.70 mmol), and Herrmann's catalyst (94 mg, 0.100 mmol) was dissolved in DMF (10 mL) and the reaction mixture was stirred at 120 °C for 4 days. Once the reaction mixture was cooled to RT, the residue was dissolved in AcOEt (50 mL) and 1M HCl (50 mL). The organic layer was separated, washed with water (50 mL x 3) and brine (50 mL), dried over MgSO4, and evaporated to dryness under reduced pressure. The residue was separated by chromatography on silica gel using hexane, 33% CH2Cl2 as the eluent, and the fraction containing compound Ph-CN-C8(p) (R f= hexane, 0.30 in 33% CH2Cl2) was collected and evaporated to dryness to give a white solid (850 mg, 1.55 mmol, 78% yield).

[0147] Synthesis of compound Ph-CN-C6(o) shown in FIG. 17E: A mixture of 2-bromobenzonitrile (364 mg, 2.00 mmol), 1H,1H,2H-perfluoro-1-octene (1.04 g, 3.00 mmol), NaOAc (246 mg, 3.00 mmol), n-Bu4NBr (548 mg, 1.70 mmol), and Herrmann's catalyst (94 mg, 0.100 mmol) was dissolved in DMF (10 mL) and the reaction mixture was stirred in a microwave reactor at 200° C. for 1 h. After the reaction mixture was cooled to RT, the residue was dissolved in AcOEt (50 mL) and 1M HCl (50 mL). The organic layer was separated, washed with water (50 mL×3) and brine (50 mL), dried over MgSO4, and evaporated to dryness under reduced pressure. The residue was separated by chromatography on silica gel using hexane, 33% CH2Cl2 as the eluent, and the fraction containing compound Ph-CN-C6(o) (R f = hexane, 0.30 in 33% CH2Cl2) was collected and evaporated to dryness to give a colorless oil (700 mg, 1.57 mmol, 78% yield).

[0148] Synthesis of compound Ph-NO2-C6(o) shown in Figure 17F: A mixture of 1-bromo-2-nitrobenzene (2.02 g, 10.0 mmol), 1H,1H,2H-perfluoro-1-octene (5.19 g, 15.0 mmol), NaOAc (1.23 g, 15.0 mmol), n-Bu4NBr (2.74 g, 8.50 mmol), and Pd(OAc)2 (112 mg, 0.499 mmol) was dissolved in DMF (10 mL) and the reaction mixture was stirred at 125 °C for 24 h. Once the reaction mixture was cooled to RT, the residue was dissolved in AcOEt (50 mL) and 1 M HCl (50 mL). The organic layer was separated, washed with water (50 mL x 3) and brine (50 mL), dried over MgSO4, and evaporated to dryness under reduced pressure. The residue was separated by chromatography on silica gel using a gradient of 1% to 5% CH2Cl2 in hexane as eluent, and the fraction containing compound Ph-NO2-C6(o) (R f = hexane, 0.55 in 33% CH2Cl2) was collected and evaporated to dryness to give a colorless oil (1.70 g, 3.64 mmol, 36% yield).

[0149] Synthesis of compound Ph-NO2-C8(o) shown in Figure 17G: A mixture of 1-bromo-2-nitrobenzene (2.02 g, 10.0 mmol), 1H,1H,2H-perfluoro-1-octene (5.19 g, 15.0 mmol), NaOAc (1.23 g, 15.0 mmol), n-Bu4NBr (2.74 g, 8.50 mmol), and Pd(OAc)2 (112 mg, 0.499 mmol) was dissolved in DMF (10 mL) and the reaction mixture was stirred at 125 °C for 24 h. Once the reaction mixture was cooled to RT, the residue was dissolved in AcOEt (50 mL) and 1 M HCl (50 mL). The organic layer was separated, washed with water (50 mL x 3) and brine (50 mL), dried over MgSO4, and evaporated to dryness under reduced pressure. The residue was separated by chromatography on silica gel using a gradient of 1% to 5% CH2Cl2 in hexane as eluent, and the fraction containing compound Ph-NO2-C8(o) (R f= hexane, 0.55 in 33% CH2Cl2) was collected and evaporated to dryness to give a white solid (3.92 g, 6.95 mmol, 69% yield).

[0150] Synthesis of compound Ph-CF3-C6(o) shown in Figure 17H: A mixture of 2-bromobenzotrifluoride (450 mg, 2.00 mmol), 1H,1H,2H-perfluoro-1-octene (1.01 g, 2.92 mmol), NaOAc (250 mg, 3.05 mmol), n-Bu4NBr (540 mg, 1.68 mmol), and Herrmann's catalyst (94 mg, 0.100 mmol) was dissolved in DMF (10 mL) and the reaction mixture was stirred in a microwave reactor at 200 °C for 1 h. Once the reaction mixture was cooled to RT, the residue was dissolved in AcOEt (50 mL) and 1M HCl (50 mL). The organic layer was separated, washed with water (50 mL x 3) and brine (50 mL), dried over MgSO4, and evaporated to dryness under reduced pressure. The residue was separated by chromatography on silica gel using hexane as eluent, and the fraction containing compound Ph-CF3-C6(o) (R f =0.50 in hexanes) was collected and evaporated to dryness to give a colorless oil (574 mg, 1.17 mmol, 59% yield).

[0151] Synthesis of compound Ph-CF3-C6(p) shown in Figure 17I: A mixture of 4-bromobenzotrifluoride (450 mg, 2.00 mmol), 1H,1H,2H-perfluoro-1-octene (1.04 g, 3.00 mmol), NaOAc (246 mg, 3.00 mmol), n-Bu4NBr (540 mg, 1.68 mmol), and Herrmann's catalyst (94 mg, 0.100 mmol) was dissolved in DMF (10 mL) and the reaction mixture was stirred at 125 °C for 24 h. Once the reaction mixture was cooled to RT, the residue was dissolved in AcOEt (50 mL) and 1M HCl (50 mL). The organic layer was separated, washed with water (50 mL x 3) and brine (50 mL), dried over MgSO4, and evaporated to dryness under reduced pressure. The residue was separated by chromatography on silica gel using hexane as eluent, and the fraction containing compound Ph-CF3-C6(p) (R f =0.50 in hexanes) was collected and evaporated to dryness to give a colorless oil (930 mg, 1.90 mmol, 95% yield).

[0152] Synthesis of compound 1-Naph-C6 shown in FIG. 14J: A mixture of 1-bromonaphthalene (1.24 g, 6.00 mmol), perfluorohexyl iodide (3.48 g, 7.80 mmol), and copper (powder, <75 μm, 1.00 g, 15.6 mmol) was dissolved in DMF (10 mL) and the reaction mixture was stirred at 120° C. for 24 h. Upon cooling the reaction mixture to RT, the residue was dissolved in AcOEt (50 mL) and 1 M HCl (50 mL). The organic layer was separated, washed with water (50 mL×3) and brine (50 mL), dried over MgSO4, and evaporated to dryness under reduced pressure. The residue was separated by chromatography on silica gel using hexane as eluent, and the fraction containing compound 1-Naph-C6 (R f =0.55 in hexanes) was collected and evaporated to dryness to give a colorless oil (1.12 g, 2.51 mmol, 42% yield).

[0153] Synthesis of compound 2-Naph-C6 shown in FIG. 14K: A mixture of 2-bromonaphthalene (1.24 g, 6.00 mmol), perfluorohexyl iodide (3.48 g, 7.80 mmol), and copper (powder, <75 μm, 1.00 g, 15.6 mmol) was dissolved in DMF (10 mL) and the reaction mixture was stirred at 120° C. for 24 h. Upon cooling the reaction mixture to RT, the residue was dissolved in AcOEt (50 mL) and 1 M HCl (50 mL). The organic layer was separated, washed with water (50 mL×3) and brine (50 mL), dried over MgSO4, and evaporated to dryness under reduced pressure. The residue was separated by chromatography on silica gel using hexane as eluent, and the fraction containing compound 1-Naph-C6 (R f =0.55 in hexanes) was collected and evaporated to dryness to give a white solid (600 mg, 1.34 mmol, 22% yield).

[0154] All electrode and cell fabrication materials were dried and then stored in an argon-filled glove box (H2O content <1 ppm, O2 content <1 ppm, MBRAUN). LiClO4 (99.99% trace metals basis, Sigma-Aldrich), stainless steel mesh (316 stainless steel, McMaster) and Whatman filter paper (Grade QM-A, pore size 2.2 μm, thickness 450 μm, Sigma Aldrich) were dried in a Buchi glass oven under active vacuum at 120 °C for 24 h. DMSO (anhydrous, >99.9%, Sigma-Aldrich) and 4-nitrophenylsulfur pentafluoride (Ph-NO2-SF5(p), 97%, Synquest) were stored in the glove box at RT.

[0155] Ketjen black (KB) electrodes were fabricated in-house by uniformly coating sonicated ink, composed of KB (AzkoNobel) powder, N-methyl-2-pyrrolidone (NMP), and polyvinylidene fluoride (PVDF) (KB:PVDF weight ratio = 80:20), onto Toray paper (TGP-H-030, Fuel cell earth). The resulting KB-coated Toray paper, after air-drying at RT, was cut into circular disks (12 mm diameter) and then dried overnight at 90 °C under active vacuum in a glass oven (Buchi).

[0156] A two-electrode Swagelok-type Li cell was constructed in an argon glove box using a dried KB cathode and a 9 mm diameter Li metal disk (0.75 mm thick, 99.9% metal base, Alfa Aesar) as the anode, which was then cooled in pure C6F for at least 3 days before use. 13 The cells were pre-stabilized by soaking in Li / Li (99%, Sigma-Aldrich). The separator (a 13 mm diameter glass fiber filter paper) was impregnated with 50 μL of electrolyte solution (as indicated in the text). The cells were left at open circuit voltage (OCV) for 5 h before galvanostatic discharge tests, which were performed by discharging the Li / Li from the OCV at the specified current density. + Constant current discharge was performed at 50° C. using a voltage window ranging from 0.1 V to a lower cutoff voltage of 1.9 V vs. 0.1 V (BioLogic VMP3 potentiostat or MPG2 workstation). After assembly, the cells were placed in an incubator (Memmert GmbH+Co.KG) for constant current discharge to be performed at 50° C. Example 3

[0157] The following examples describe high energy Li primary battery cathodes that utilize defluorination of perfluorinated groups, such as pentafluorosulfanyl (SF5) groups.

[0158] Intrinsic electroactivity of R-Ph-SF5 molecules: It is demonstrated that the design strategy for SF5-containing compounds can be applied to a variety of R group functionalities and positions, and the number of perfluorinated SF5 groups is not limited to one. For example, a suitable reactant structure containing a sulfur pentafluoride group is shown in Figure 18. To investigate the intrinsic redox behavior, Figures 19A and 19B show the electroactivity of 0.1M R-Ph-SF5-containing cells at 40 μA / cm, with the capacity normalized to the weight of the reactant (Figure 19A) and the electrons reacted per molecule (Figure 19B). 2 The cell was discharged at 40 μA cm using 0.1 M R-Ph-SF5 / 0.1 M LiClO4 / DMSO as the catholyte and Ketjen black as the cathode substrate. -2 The cells were then discharged at 50°C. The cells were tested at 50°C to maximize capacity. Unsubstituted Ph-SF5 and Ph-I-SF5 showed a Li / Li charge across a single plateau. + A moderate voltage of about 2.5 V was obtained for Li / Li. Increasing the Hammett coefficient of the electron-withdrawing functional group to -NO2 in the meta (m) or para (p) positions (0.71 or 0.78 compared to 0.18 for -I in para) resulted in higher discharge voltages. The highest cell voltage was obtained with -NO2 in the para (p) position, with a Li / Li + A three-stage discharge profile with plateaus at 2.9, 2.3, and 2.1 V was obtained, with a total capacity of 8e - / molecule(861mAh g R-Ph-SF5 -1 ) was.

[0159] Next, the discharge of a reactant containing two -SF5 groups, i.e., Br-Ph-2SF5, was investigated at RT, and the results are shown in Figures 20A-20B. The cell was discharged at 40 μA cm using 0.1 M Br-Ph-2SF5 / 0.1 M LiClO4 / DMSO as the catholyte and carbon foam as the cathode substrate. -2 and discharged at RT. The Li-Br-Ph-2SF5 cell was charged to Li / Li + The two discharge plateaus at 2.6 and 2.2 V vs. -At the end of discharge, the low voltage (Li / Li + A tail (<2.0 V vs. ) was observed, suggesting the continued reduction of aromatic constituents. Overall, 1138 mAh / g Br-Ph-2SF5 A total capacity of 1000 μm was obtained.

[0160] Products of p-NO2-Ph-SF5 discharge: Next, the discharge products and performance of Li-R-Ph-SF5 cells were investigated in detail using p-NO2-Ph-SF5 (hereafter "p" will be omitted) as an exemplary system. To investigate the conversion process in detail, 0.1M NO2-Ph-SF5 was discharged to various termination voltages (FIG. 21A), after which the cathode and / or electrolyte were extracted for analysis. Li / Li + Between 2.54 and 2.38 V vs. , the cathode consists of cubic crystallites of about 270 ± 50 nm (Figure 21B), which is consistent with the XPS F 1s spectrum. [ka] The two CF peaks at 688.4 and 686.4 eV are from the polyvinylidene fluoride (PVDF) binder. Considering the electronically insulating nature of LiF, the energy-minimized structure and large particle size suggest that the LiF particles grow via a solution-mediated process. Although the amount of solid sulfur products in the S 2p spectrum of the cathode was negligible after the high-voltage plateau (<0.1%, Figure 21D), UV-vis spectroscopy and visual analysis revealed that most of the sulfur was present in solution as polysulfides and S8 2- It was confirmed that the Li / Li ratio predominates (Figures 21E-21F). The data collectively indicate that this high voltage plateau corresponds to the near stoichiometric defluorination of all 5F ligands in Ph-NO2-SF5, which is a process that liberates S intermediates from the parent molecule, which then undergo polymerization reactions in solution. + 2.07V (approximately 1 e -Upon further discharge to 300 s, polysulfide production continued and the S content of the cathode increased slightly (to about 0.8%, FIG. 21D).

[0161] Li / Li + Upon full discharge to 1.90 V vs. 100 V, nearly complete disappearance of all species was detected by UV-vis (Figure 21E), and XPS showed a moderate increase in the S and N content of the cathode (to about 1.5 and 1.3%, respectively, Figure 21D). Nitro-functionalized aromatics were synthesized in DMSO with short chains (S2 2- ) reacts with polysulfides, leaving NO2 as the leaving group. - The O content in the cathode also tends to decrease with Li / Li, which may explain the lack of S in the solid phase at the discharged cathode and the retention of reduced S in the liquid phase with a slight increase in N. +The charge-dissipation potential increased from 16.8% to 27.0% between 2.07 and 1.90 V vs. 100 V (Figure 21D), while the corresponding SEM images showed the nucleation of a new phase with a spherical morphology (Figure 21B), which was confirmed by energy dispersive X-ray (EDX) analysis to be O-rich and N, F, and S-poor. Significantly, headspace analysis of the cell by mass spectrometry and gas chromatography (Figures 22A-22B, respectively) ruled out the formation of NO, NO2, or NO. A background comparison was also performed with headspace gas from a cell with the same electrolyte and cathode (without Li) after standing at 50 °C for 3 days. The peaks at 4.4-4.5 min and 8 min in Figure 22B are due to the valve switch. Furthermore, the cell discharged with the pressure transducer showed only slight gas evolution of any kind (Figure 22C). While the exact mechanism of multielectron NO2-Ph-SF5 reduction is complex, the overall mechanism indicates widespread activation and reduction of SF, SS, CS, and NO bonds resulting in solid and liquid products that accumulate throughout the cell. The solid line in Figure 22C is the predicted pressure baseline, extrapolated from a linear fit of the cell pressure profile during post-discharge rest (10 h). The cell in Figure 22C was run at 40 μA cm with 150 μL of 0.1 M NO2-Ph-SF5 / 0.1 M LiClO4 / DMSO electrolyte and a KB electrode. -2 and discharged at 50°C.

[0162] Discharge performance of Li-NO2-Ph-SF5 cells: The electrochemical performance was investigated as a function of reactant concentration to evaluate its feasibility as a highly concentrated catholyte. Figure 23A shows the discharge current of 40 μA / cm2 at concentrations from 1 to 5 M. 2 and galvanostatic discharge at 50 °C, where the capacity is normalized to the weight of NO2-Ph-SF5 as an intrinsic measure of reactant utilization. Discharges at concentrations of 1.0–2.0 M yielded 818 and 786 mAh g, respectively. NO2-Ph-SF5 -1An accessible capacity of 1.0 mAh g−1 was obtained, with a similar discharge profile. Further increase in concentration (≥3M) showed the disappearance of the lower voltage plateau at about 2.1 V vs Li / Li+, with a capacity of 544 mAh g−1 at 5.0M. NO2-Ph-SF5 -1 A capacity of 10 ...

[0163] Despite the lower utilization per molecule, increasing the concentration allows for improved cell-level metrics, with the areal capacity of the cell in Figure 23A ranging from 5.8 to 19.1 mAh cm between 1.0 and 5.0 M. -2 To accurately represent the cell performance based on gravimetric measurements, a normalization was performed based on the weight of all cell materials (i.e., NO2-Ph-SF5 + electrolyte + carbon cathode + consumed Li) (hereafter referred to as the "substack") excluding only the current collector, separator, binder, and cell housing. Figure 23C shows the current at 0.1 mA cm -2 The capacitance and gravimetric energy of these substacks at a slightly higher current of 1.2 e per molecule are shown. - As the concentration increases from 3M to 4M, the capacity increases to 292 mAh g サブスタック -1 from 362mAh g サブスタック -1 At 4.5 M, the gain was 1085 Wh kg サブスタック -1The maximum gravimetric energy of 1.0 mS cm was obtained. The capacity and energy decreased with concentration above 4.5 M, which was due to a decrease in the supporting solvent (DMSO, about 16 wt% of the catholyte at 5 M), which resulted in an ionic conductivity of 6.4 mS cm from 0.1 M to 5 M. -1 to 0.6 mS cm -1 This is due to the significant decrease in the DMSO content (Figure 24). In addition, as the DMSO content decreases, the ability to solubilize LiF decreases, and the passivation effect of the electrode becomes more severe. The rate capacity of the cell at 4.0 M concentration and 50 °C is shown in Figure 23D. The capacity ranged from 0.3 to 1.0 mA cm. -2 (0.01C~0.04C) approx. 362mAh g サブスタック -1 remains constant at 3 mA cm -2 (0.12C), showing excellent rate capability. Of crucial importance for primary battery applications, Figure 25 shows that the as-assembled Li-NO2-Ph-SF5 cell stored at 50 °C for 30 days showed no capacity loss on subsequent discharge, and the cell also showed only slight voltage decay upon interruption at partial discharge depth and storage for 10 to 30 days, showing good shelf life characteristics.

[0164] To compare performance with state-of-the-art primary batteries, Li-CF x The cells were assembled and tested. The cell mass breakdown is shown in Figure 26A. Typical mass fractions of electrolyte to active solids in commercial cells range from 0.7 to 1.3, which is a low electrolyte loading that is difficult to achieve in-house. As a result, the Li-CF x Cell (20.4±2.3mg CF x , loading 11.5±1.3mg cm -2 ) were tested in a flooded electrolyte configuration, but standardized assuming a 1:1 electrolyte:cathode mass ratio as determined by commercially available standards. In Li-NO2-Ph-SF5 cells, the active material is in the liquid phase, and therefore design considerations favor a substantially larger electrolyte-to-solids ratio of about 8:1 w / w (carbon is electrochemically inactive), with a concentration of 5 mg cm for a 4 M concentration. -2of carbon and about 28 mg cm -2 The Ragawney plot (Figure 26B) shows that the Li-NO2-Ph-SF5 cell outperforms the Li-CF x This indicates that the sub-stack level performance equivalent to that of a single cell is reached (approximately 15 W kg サブスタック -1 Approximately 1000Wh kg サブスタック -1 ). The averages and error bars (representing standard deviation) are based on three cells each. These values ​​are in contrast to the sub-stack measurements, which exclude the inert electrolyte / carbon, giving a total energy density of 1845Wh kg 活性 -1 (Li-NO2-Ph-SF5) and 2050Wh·kg 活性 -1 (Li-CF x ) theoretical active mass value. These figures show, first, that both cell formulations show a significant drop in gravimetric energy when the inert mass (electrolyte + carbon) is accounted for based on a more realistic substack, and, second, that the Li-NO2-Ph-SF5 cell with liquid reactants shows proportionally higher active mass utilization, which in turn makes comparable or higher cell energies practically possible. This gain is comparable to the theoretical active mass value of the Li-CF x This stems from the ability to minimize electrolyte deadweight compared to Li-NO2-Ph-SF5 cells (both cells utilize equivalent inert C). Additionally, Li-NO2-Ph-SF5 cells offer a moderate power output (50-100 W kg サブスタック -1 ) with Li-CF x These gains are due to the limited ionic conductivity of the NO2-Ph-SF5 based electrolyte, which is why higher power output (>150 W kg) is not possible for this particular formulation. サブスタック -1 ) decreases.

[0165] Hybrid solid-liquid cell designs: Li-NO2-Ph-SF5 and Li-CF xThe chemical compatibility and voltage matching of NO2-Ph-SF5:CF3 creates new possibilities for designing hybrid cell concepts that exceed the gravimetric energy of any known formulation. To demonstrate this, a mixture of NO2-Ph-SF5:CF3 in a mass ratio of approximately 2:1 was x A cell was designed containing (FIG. 26A). The total substack percentage of active material was Li-CF x (about 50%) or Li-NO2-Ph-SF5 cells (about 70%). The hybrid cell had a maximum current of 0.1 mA cm -2 and 421 mAh g at 50°C サブスタック -1 A gravimetric capacity of ≤362 mAh g was obtained for each individual cell. サブスタック -1 , Fig. 26C). x "Substack" is a CF x + electrolyte + carbon + consumed Li, and for hybrid cells, the weight of NO2-Ph-SF5 is also included. 5W kg サブスタック -1 at 1195Wh kg サブスタック -1 The gravimetric energy reaching x This is about a 20% improvement over the CF (Fig. 26B). SEM images of the discharged cells (Fig. 26D) show that the CF x On graphite flakes, CF x The hybrid cells show the formation of LiF crystallites that are not present in the pure LiF cells, further confirming the utilization of both solid and liquid capacitance. The hybrid cells are based on commercially available CF x Note that a powder blend is utilized, which does not necessarily provide the optimal surface area to accommodate NO2-Ph-SF5 discharge. The theoretical predicted energy of the hybrid cell is computed in Figure 27, with the maximum performance for 5M reactants occurring at approximately 1:1.1 NO2-Ph-SF5:CF x Mass ratio and capacity: 627mAh g, an increase of approximately 50% over the figures above that have actually been achieved so far サブスタック -1The shaded area in Figure 27 (solid component (CF x +C) is greater than the weight of the liquid) is considered impractical because it becomes difficult for the electrolyte to adequately wet the electrodes under these conditions. The maximum attainable capacity of Figure 26C (with 4M NO2-Ph-SF5) is labeled "attained" in Figure 27.

[0166] Rechargeability of Li-NO2-Ph-SF5 cells: We next investigated the potential of Li-NO2-Ph-SF5 cells as secondary (i.e., rechargeable) batteries. First, a cell containing 0.1M NO2-Ph-SF5 was charged at 0.3 mA / cm 2 The discharge rate was then increased to 0.04 mA / cm to promote the formation of small particle size LiF. 2 The stability of DMSO is relatively limited (Li / Li + <4.5V for Li / Li + Another solvent, namely ethylene carbonate / dimethyl carbonate (EC / DMC, 1:1 v / v), was also tested. The profiles of the first discharge at 50 °C and the two subsequent cycles are shown in Figure 28. To minimize the effect of solvent decomposition, the cells containing EC / DMC were charged to Li / Li + The cells containing DMSO were cycled between 1.5 and 4.6 V vs. Li / Li + The cells were cycled between 1.9 and 3.9 V vs. 1.0 V. In the second discharge, the cells with DMSO discharged at 0.26 mAh / cm 2 or 2.2e - The battery showed multiple voltage plateaus similar to those observed during the first discharge (after the high voltage plateau), corresponding to a capacity of 1.3 e / molecule. A similar discharge profile was maintained during the third discharge, but the capacity was reduced to approximately 1.3 e - The cell containing EC / DMC had a higher reversible capacity (0.47 mAh / cm 2 or 3.9e - / molecule), but has a ramping voltage rather than a multi-plateau profile, which is attributed to the instability of polysulfides with carbonate-based electrolytes. The first discharge was 0.3 mA / cm 2 All cells were discharged at 50 °C using 0.1 M NO2-Ph-SF5 / 0.1 M LiClO4 / DMSO as catholyte and Ketjen black as cathode substrate. Overall, the electrochemical activity observed during the second and third discharges indicates that the reduction of NO2-Ph-SF5 is partially reversible and occurs mainly in the lower voltage region (after the defluorination reaction), with a kinetic energy of about 2–3 e - This suggests that it has a capacity of 1 / molecule.

[0167] Alternative anode metals: To demonstrate the compatibility of the NO2-Ph-SF5 catholyte with non-Li anodes, Na and Ca were investigated as examples of monovalent and divalent anode metal species, respectively. The discharge profiles at 50 °C of Na-NO2-Ph-SF5 cells containing DMSO or 4M NO2-Ph-SF5 / 0.2M NaTFSI in EC / propylene carbonate (PC) as catholyte are shown in Figure 29A. The cells containing DMSO showed a higher discharge current than the Na / Na + 2.3mAh / cm at approximately 2.2V 2 While the cell containing EC / PC showed a discharge capacity of 100% compared to the cell containing Na / Na + All cells were discharged at 0.3 mA / cm using carbon foam as the cathode substrate. 2 and discharged at 50 °C. The discharge products of the EC / PC-containing cells were characterized using SEM in FIG. 29B. Small particles were observed on the discharged carbon substrate, whose composition was found to be mainly Na and F from EDX analysis. The decrease in discharge capacity of the Na-NO2-Ph-SF5 cell compared to its Li counterpart is likely due to the decreased stability of Na metal to the solvent.

[0168] Considering the instability of Na metal with DMSO, the reversibility of the Na-NO2-Ph-SF5 cell was investigated at RT using EC / DMC solvent. Similar to the Li cell, a low reactant concentration of 0.1 M was used and the cell was first charged at RT with 0.3 mA / cm 2 Then, discharge at a high rate of Na / Na + 0.02mA / cm between 1.2 and 4.5V 2 The battery was cycled at 1000 mAh / g (Figure 30). The first discharge showed only one voltage plateau before reaching the lower cutoff voltage, resulting in a capacity of 441 mAh / g. NO2-Ph-SF5 During the second discharge, the voltage profile sloped down to 380 mAh / g NO2-Ph-SF5 Considering that some reactants likely remained unreacted after the first discharge, which may contribute to the capacity during the second discharge, the total capacity of the two discharges (821 mAh / g Ph-NO2-SF5 ) to the theoretical capacity of the high voltage plateau (538–646 mAh / g, assuming 5–6 electron transfers). NO2-Ph-SF5 The total discharge capacity of the first two discharges exceeds the theoretical value, which is about 200 mAh / g. Ph-NO2-SF5 This suggests that the capacity of the battery is reversible, as seen during the third discharge of >200 mAh / g / g Ph-NO2-SF5 This is further confirmed by the capacity of 0.01 V (where the effect of unreacted NO2-Ph-SF5 can be excluded), demonstrating that the high voltage discharge of the NO2-Ph-SF5 catholyte is potentially rechargeable when a weaker bonding metal, e.g., Na, is used as the anode.

[0169] The discharge of a NO2-Ph-SF5 catholyte containing Ca as a divalent metal anode is shown in Figure 31. The cell utilized 4M NO2-Ph-SF5 / 0.2M CaTFSI / DMSO as the catholyte and discharged at 0.04 mA / cm 2 Discharged at 50°C in Ca / Ca 2+ Starting at a voltage of 0.8 V, 2A total capacity of 10 ...

[0170] Although several embodiments of the invention have been described and illustrated herein, various other means and / or structures for carrying out the functions and / or obtaining one or more of the results and / or advantages described herein will readily occur to those skilled in the art, and each of such variations and / or modifications is deemed to be within the scope of the invention. More generally, all parameters, dimensions, materials, and configurations described herein are meant to be exemplary, and those skilled in the art will readily appreciate that the actual parameters, dimensions, materials, and / or configurations will depend on the particular application or applications for which the teachings of the invention are used. Those skilled in the art will recognize or be able to ascertain, using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. Thus, the foregoing embodiments are presented by way of example only, and it should be understood that the invention may be practiced otherwise than as specifically described and claimed, within the scope of the appended claims and equivalents thereto. The invention is directed to each individual feature, system, product, material, kit, and / or method described herein. In addition, any combination of two or more such features, systems, products, materials, kits, and / or methods is included within the scope of the present invention, if such features, systems, products, materials, kits, and / or methods are not mutually inconsistent.

[0171] All definitions defined and used herein should be understood to supersede any dictionary definitions, definitions in documents incorporated by reference, and / or ordinary meanings of the defined terms.

[0172] The indefinite articles "a" and "an," as used in the specification and claims, unless expressly stated to the contrary, should be understood to mean "at least one."

[0173] The phrase "and / or," as used herein and in the claims, should be understood to mean "either or both" of the elements so connected, i.e., elements that are conjunctive in some cases and disjunctive in other cases. Multiple elements listed with "and / or" should be interpreted in the same manner, i.e., "one or more" elements so connected. Other elements may optionally be present other than the elements specifically identified by the "and / or" clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to "A and / or B," when used with open-ended language such as "comprising," may refer in one embodiment to only A (including elements other than B, as appropriate), in another embodiment to only B (including elements other than A, as appropriate), in yet another embodiment to both A and B (including other elements, as appropriate), and so forth.

[0174] When used in the specification and 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" should be interpreted as being inclusive, i.e., including at least one of, but also including more than one of, an element or a list of elements, and including additional items not listed, if necessary. Only terms expressly indicating the contrary, such as "only one of" or "exactly one of," or "consisting of," when used in the claims, indicate the inclusion of exactly one element in an element or list of elements. In general, the term "or," when used herein, should be interpreted as indicating exclusive alternatives (i.e., "one or the other, but not both") only when followed by an exclusive term, such as "any of," "one of," "only one of," or "exactly one of." "Consisting essentially of," when used in the claims, shall have its ordinary meaning as used in the field of patent law.

[0175] As used in this specification and claims, the phrase "at least one" referring to a list of one or more elements should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed in the list of elements, and not excluding any combination of elements in the list of elements. This definition also allows that elements other than those specifically identified in the list of elements to which the phrase "at least one" refers may optionally be present, whether related or unrelated to the specifically identified elements. Thus, as a non-limiting example, "at least one of A and B" (or, equivalently, "at least one of A or B" or, equivalently, "at least one of A and / or B") can refer in one embodiment to at least one, and optionally more than one, A (optionally including elements other than B), where B is absent; in another embodiment to at least one, and optionally more than one, B (optionally including elements other than A); in yet another embodiment to at least one, and optionally more than one, A, and at least one, and optionally more than one, B (optionally including other elements); etc.

[0176] Also, unless expressly stated to the contrary, in any method claimed herein that includes more than one step or act, it should be understood that the order of the method steps or acts is not necessarily limited to the order in which the method steps or acts are described.

[0177] In the claims and the above specification, all transitional phrases, such as "comprising," "including," "carrying," "having," "containing," "involving," "holding," "composed of," and the like, are understood to be open-ended, i.e., meant to include, but not be limited to. Only the transitional phrases "consisting of" and "consisting essentially of" shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.

Claims

1. a first electrode comprising an alkali metal and / or alkaline earth metal; a second electrode; and Halogenated compounds containing at least one sulfur pentafluoride group linked to a conjugated system 1. An electrochemical cell comprising: The specific energy of the electrochemical cell is 2200 Wh / kg 反応物 Equal to or higher than 2800Wh / kg 反応物 and said reactant is said halogenated compound.

2. a first electrode comprising an alkali metal and / or alkaline earth metal; a second electrode; and Halogenated compounds containing at least one sulfur pentafluoride group linked to a conjugated system 1. An electrochemical cell comprising: The total capacity of the electrochemical cell is 1000 mAh / g 反応物 equal to or greater than 1400 mAh / g 反応物 and said reactant is said halogenated compound.

3. a first electrode comprising an alkali metal and / or alkaline earth metal; a second electrode; and Halogenated compounds containing at least one sulfur pentafluoride group linked to a conjugated system 1. An electrochemical cell comprising: The halogenated compound is 【Chemistry 7】 An electrochemical cell selected from the group consisting of:

4. a first electrode comprising an alkali metal and / or alkaline earth metal; a second electrode; and An electrochemical cell comprising a halogenated compound containing more than one sulfur pentafluoride group bonded to a conjugated system.

5. a first electrode comprising an alkali metal and / or alkaline earth metal; a second electrode; and electrolyte solution 1. An electrochemical cell comprising:

1. An electrochemical cell, wherein the electrolyte solution comprises a halogenated compound at a concentration greater than or equal to 0.1 mM and less than or equal to 50 mM at 25° C. and 1 atmosphere, the halogenated compound comprising at least one sulfur pentafluoride group bonded to a conjugated system.

6. a first electrode comprising an alkali metal and / or alkaline earth metal; a second electrode; and liquid electrolyte 1. An electrochemical cell comprising: Electrochemical cell wherein the liquid electrolyte is a halogenated compound containing at least one sulfur pentafluoride group bonded to a conjugated system.

7. 7. The electrochemical cell of claim 1, wherein the first electrode comprises an alkali metal.

8. 7. The electrochemical cell of claim 1, wherein the first electrode comprises lithium and / or sodium.

9. 7. The electrochemical cell of claim 1, wherein the alkali metal comprises lithium.

10. 7. The electrochemical cell of claim 1, wherein the second electrode comprises carbon and / or a metal.

11. 7. The electrochemical cell of claim 1, wherein the second electrode comprises carbon monofluoride.

12. 7. The electrochemical cell of claim 1, wherein the second electrode comprises graphene, graphene oxide, graphite, a carbonized material, a carbon nanomaterial, carbon powder, a carbon gas diffusion layer, Pt, Ni, Pd, Fe, Co, Au, and / or Cu.

13. 7. An electrochemical cell according to any one of claims 1 to 6, wherein the conjugated system comprises at least one optionally substituted aromatic group.

14. 14. The electrochemical cell of claim 13, wherein the at least one optionally substituted aromatic group comprises benzene.

15. 5. The electrochemical cell of claim 1, further comprising an electrolyte solution.

16. 16. The electrochemical cell of claim 15, wherein the electrolyte solution comprises the halogenated compound.

17. 16. The electrochemical cell of claim 15, wherein the electrolyte solution comprises the halogenated compound at a concentration greater than or equal to 100 mM and less than or equal to 5 M at 25° C. and 1 atmosphere.

18. An electrochemical cell as described in any one of claims 1 to 4, or an electrochemical cell as described in claim 5, further comprising an electrolyte solution, wherein the electrolyte solution comprises dimethyl sulfoxide, glyme, carbonate, tetrahydrofuran, dimethylacetamide, dimethylformamide, and / or an ionic liquid.

19. The electrochemical cell according to claim 1, further comprising an electrolyte solution, wherein the electrolyte solution is LiClO. ４ , LiPF ６ , LiBF ４ , LiCF ３ SO ３ , LiNO ３ , LiI, LiBr, lithium bis(oxalato)borate, lithium bis(fluorosulfonyl)imide, and / or lithium bis(trifluoromethanesulfonyl)imide.

20. The electrochemical cell of any one of claims 1 to 6, wherein the electrochemical cell is a primary battery.

21. The electrochemical cell according to any one of claims 1 to 6, wherein the electrochemical cell is a secondary battery.

22. 7. The electrochemical cell of claim 1, wherein the second electrode comprises a halogenated layer.

23. 7. The electrochemical cell of any one of claims 1 to 3, 5 and 6, wherein the halogenated compound comprises one sulfur pentafluoride group attached to the conjugated system.

24. 7. The electrochemical cell of claim 1, wherein the halogenated compound comprises two sulfur pentafluoride groups attached to the conjugated system.

25. The halogenated compound is 【Chemistry 8】 【Chemistry 9】 7. The electrochemical cell of claim 1, 2, 5, or 6, selected from the group consisting of:

26. The specific energy of the electrochemical cell is 2200 Wh / kg 反応物 Equal to or higher than 2800Wh / kg 反応物 7. The electrochemical cell of claim 2, wherein the reactant is the halogenated compound.

27. The total capacity of the electrochemical cell is 1000 mAh / g 反応物 equal to or greater than 1400 mAh / g 反応物 7. The electrochemical cell of any one of claims 1 and 3 to 6, wherein the reactant is the halogenated compound.

28. 16. The electrochemical cell of claim 15, wherein the electrolyte solution comprises the halogenated compound at a concentration greater than or equal to 0.1 mM and less than or equal to 50 mM at 25° C. and 1 atmosphere pressure.

29. 5. The electrochemical cell of claim 1, wherein the halogenated compound is a liquid electrolyte.

30. 1. A method for reducing a halogenated compound, comprising: Providing an electrochemical cell according to any one of claims 1 to 6; discharging the electrochemical cell; wherein the discharging step comprises oxidizing at least a portion of the alkali metal and / or alkaline earth metal and reducing at least a portion of the halide compound.

31. 31. The method of claim 30, wherein the halogenated compound is reduced by equal to or greater than six electrons.

32. 31. The method of claim 30, wherein the halogenated compound is reduced by equal to or greater than eight electrons.

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