Classifications

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  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/381—Alkaline or alkaline earth metals elements
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  • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
  • H01M4/381—Alkaline or alkaline earth metals elements
  • H01M4/382—Lithium
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  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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  • H01M2004/028—Positive electrodes
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• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the halogenated compound comprises at least one sulfur pentahalide (e.g., pentafluoride) group associated with a conjugated system.
• sulfur pentahalide e.g., pentafluoride
• Li primary batteries are in increasing demand for long-duration standalone systems such as unmanned vehicles, space applications, and implantable/portable medical devices. Owing to the light weight of lithium (Li) and its low electrochemical potential, Li anodes enable construction of batteries with high gravimetric and volumetric energy densities.
• Li primary batteries such as Li-SOCh, Li-carbon monofluoride (Li-CF X ), and Li-Mn02 systems with theoretical energy densities of 1470, 2180, and 1005 Wh/kg re actant, respectively, hold increasing market share.
• Accidental voltage reversal in such Li-containing batteries can result thermal runaway conditions, such as cell venting or overheating.
• Li-SOCh batteries utilize liquid SOCh, which is highly toxic if vented or leaked, thus such batteries are not suitable for civil applications where frequent handling and safe transport or storage is essential.
• Li-CF X batteries have improved safety, but face challenges such as poor high-rate performances and voltage delay at the initial discharge, thus being only suitable for low-to-medium rate applications. Accordingly, improved systems, articles, and methods related to primary batteries are desirable.
• the halogenated compound comprises at least one sulfur pentahalide (e.g., pentafluoride) group associated with a conjugated system.
• sulfur pentahalide e.g., pentafluoride
• the subject matter of the present invention involves, in some cases, interrelated products, alternative solutions to a particular problem, and/or a plurality of different uses of one or more systems and/or articles.
• an electrochemical cell comprising 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 associated with a conjugated system.
• an electrochemical cell comprises 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, wherein the liquid electrolyte comprises a halogenated compound, and wherein the halogenated compound comprises a sulfur pentafluoride group associated with a conjugated system.
• a method of reducing a halogenated compound comprising discharging an electrochemical cell, wherein the electrochemical cell comprises an alkali metal and/or an alkaline earth metal and the halogenated compound.
• discharging comprises oxidizing at least a portion of the alkali metal and/or the alkaline earth metal and reducing at least a portion of the halogenated compound such that the halogenated compound is reduced by greater than six electrons.
• a method of reducing a halogenated compound comprises providing a system comprising a first electrode comprising an alkali metal and/or an alkaline earth metal, a second electrode, and the halogenated compound, wherein the halogenated compound comprises at least one sulfur pentafluoride group associated with a conjugated system.
• the method comprises discharging the system, wherein discharging comprises oxidizing at least a portion of the alkali metal and reducing at least a portion of the halogenated compound.
• an electrochemical cell comprises 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 associated with a conjugated system, wherein a specific energy of the electrochemical cell is greater than or equal to 2200 Wh/kg re actant and less than or equal to 2800 Wh/kg re actant, wherein the reactant is the halogenated compound.
• an electrochemical cell comprises 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 associated with a conjugated system, wherein a total capacity of the electrochemical cell is greater than or equal to 1000 mAh/greactant and less than or equal to 1400 mAh/greactant, wherein the reactant is the halogenated compound.
• an electrochemical cell comprises 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 associated with a conjugated system, wherein the halogenated compound is selected from the group consisting of:
• an electrochemical cell comprises 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 associated with a conjugated system.
• an electrochemical cell comprises a first electrode comprising an alkali metal and/or an alkaline earth metal, a second electrode, and an electrolyte solution, 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 atm, and wherein the halogenated compound comprises at least one sulfur pentafluoride group associated with a conjugated system.
• an electrochemical cell comprises a first electrode comprising an alkali metal and/or an alkaline earth metal, a second electrode, and a liquid electrolyte, wherein the liquid electrolyte is a halogenated compound comprising at least one sulfur pentafluoride group associated with a conjugated system.
• FIG. 1A shows, according to some embodiments, a schematic diagram of electrochemical cell
• FIG. IB shows, according to some embodiments, a schematic diagram of an electrochemical cell comprising an alkali metal ion and/or an alkaline earth metal ion;
• FIG. 1C shows, according to some embodiments, a schematic diagram of an electrochemical cell comprising a reduced halogenated compound
• FIG. ID shows, according to some embodiments, a schematic diagram of an electrochemical cell comprising a halogenation layer
• FIG. 2 shows, according to some embodiments, a series of non-limiting halogenated compounds
• FIG. 3 shows, according to some embodiments, a series of non-limiting structures of Rp-containing fluoro-aromatics
• FIG. 4 shows, according to some embodiments, a general synthetic scheme to obtain Rp-containing fluoro-aromatics
• FIG. 5 shows, according to some embodiments, galvanostatic discharge profiles of Ri -containing fluoro-aromatics
• FIGs. 6A-6C shows, according to some embodiments, galvanostatic discharge profiles of control group fluorinated reactants
• FIG. 7A shows, according to some embodiments, galvanostatic discharge profiles of a lithium (Li) cell with 0.1 M Ph-CN-C8 (p);
• FIG. 7B shows, according to some embodiments, galvanostatic discharge profiles of a Li cell with 0.1 M Ph-NO 2 -C6 (o);
• FIG. 7C shows, according to some embodiments, galvanostatic discharge profiles of a Li cell with 0.1 M Ph-NO 2 -C8 (o);
• FIG. 8A shows, according to some embodiments, galvanostatic discharge profiles of a Li cell with 0.1 M Ph-NO 2 -C6 (o);
• FIG. 8B shows, according to some embodiments, the galvanostatic discharge profile of a Li cell with 0.1 M Ph-NO 2 -C8 (o);
• FIG. 9A shows, according to some embodiments, a powder X-ray diffraction (XRD) pattern of the fully discharged Kejten black (KB) electrode of a Li-Ph-NO 2 -C6 (o) cell;
• XRD powder X-ray diffraction
• FIG. 9B shows, according to some embodiments, a powder XRD pattern of the fully discharged KB electrode of a Li-Ph-CN-C8 (p) cell;
• FIG. 10A shows, according to some embodiments, a scanning electron microscopy (SEM) image of a fully discharged KB electrode in a Li-Ph-CN-C8 (p) cell at 0.04 mA/cm 2 ;
• SEM scanning electron microscopy
• FIG. 10B shows, according to some embodiments, a SEM image of a fully discharged KB electrode in a Li-Ph-CN-C8 (p) cell at 0.3 mA/cm 2 ;
• FIG. 10C shows, according to some embodiments, a SEM image of a fully discharged KB electrode in a Li-Ph-CN-C8 (p) cell at 0.5 mA/cm 2 ;
• FIG. 11 shows, according to some embodiments, the galvanostatic discharge profile of a Li cell with 0.1 M fluoro-aromatic reactants comprising naphthalene functionalized with a fluoroalkane;
• FIG. 12A shows, according to some embodiments, the galvanostatic discharge profile of a Li cell with 0.1 M Ph-NO 2 -SFs (p), at room temperature (RT);
• FIG. 12B shows, according to some embodiments, the galvanostatic discharge profile of a Li cell with 0.1 M Ph-NO 2 -SF 5 (p), at 50 °C;
• FIGs. 13A-13C show, according to some embodiments, SEM images of fully discharged Ph-NO 2 -SFs cells;
• FIG. 14A shows, according to some embodiments, the galvanostatic discharge profile of high concentration PI1-NO2-SF5 cells at 50 °C;
• FIG. 14B shows, according to some embodiments, the galvanostatic discharge profile of 4 M PI1-NO2-SF5 cells at 50 °C with a 15 mm diameter carbon cathode;
• FIG. 14C shows, according to some embodiments, the galvanostatic discharge profile of 4 M PI1-NO2-SF5 cells at RT;
• FIG. 14D shows, according to some embodiments, the galvanostatic discharge profile of 4 M PI1-NO2-SF5 cells at 50 °C;
• FIG. 15 shows, according to some embodiments, the attained energy density of Ph- NO2-SF5 cells in comparison with CF X systems
• FIG. 16 shows, according to some embodiments, a Ragone plot comparing the discharge performances of Li-fluoro-aromatic cells and Li-CF X cells at 50 °C;
• FIG. 17A shows, according to some embodiments, a scheme of the synthesis of the compound Ph-H-C6;
• FIG. 17B shows, according to some embodiments, a scheme of the synthesis of the compound Py-C6
• FIG. 17C shows, according to some embodiments, a scheme of the synthesis of the compound Ph-CN-C6 (p);
• FIG. 17D shows, according to some embodiments, a scheme of the synthesis of the compound Ph-CN-C8 (p);
• FIG. 17E shows, according to some embodiments, a scheme of the synthesis of the compound Ph-CN-C6 (o);
• FIG. 17F shows, according to some embodiments, a scheme of the synthesis of the compound PI1-NO2-C6 (o);
• FIG. 17G shows, according to some embodiments, a scheme of the synthesis of the compound PI1-NO2-C8 (o);
• FIG. 17H shows, according to some embodiments, a scheme of the synthesis of the compound PI1-CF3-C6 (o);
• FIG. 171 shows, according to some embodiments, a scheme of the synthesis of the compound PI1-CF3-C6 (p);
• FIG. 17J shows, according to some embodiments, a scheme of the synthesis of the compound 1-Naph-C6.
• FIG. 17K shows, according to some embodiments, a scheme of the synthesis of the compound 2-Naph-C6.
• FIG. 18 shows, according to some embodiments, a series of non-limiting structures of halogenated compounds comprising a sulfur-pentafluoride group;
• FIG. 19A shows, according to some embodiments, galvanostatic discharge profiles of R-Ph-SFs reactants with capacities normalized to weight of the reactants;
• FIG. 19B shows, according to some embodiments, galvanostatic discharge profiles of R-Ph-SFs reactants with capacities normalized to number of electron transfer per molecule
• FIG. 20A shows, according to some embodiments, a galvanostatic discharge profile of Br-Ph-2SFs with capacities normalized to weight of the reactant
• FIG. 20B shows, according to some embodiments, a galvanostatic discharge profile of Br-Ph-2SFs with capacities normalized to number of electron transfer per molecule
• FIG. 21A shows, according to some embodiments, a discharge profile of NO2-PI1-SF5 under reactant-limited conditions with different cell termination voltages
• FIG. 2 IB shows, according to some embodiments, SEM images of carbon cathodes from cells discharged to 2.38 or 1.90 V vs. Li/Li + ;
• FIG. 21C shows, according to some embodiments, high resolution F Is X-ray photoelectron spectroscopy (XPS) spectra of discharged electrodes
• FIG. 2 ID shows, according to some embodiments, XPS survey spectra (left) with corresponding F, O and S atomic percentage (right);
• FIG. 21E shows, according to some embodiments, ultraviolet-visible (UV-vis) spectra of extracted electrolyte from discharged cells as a function of termination voltage
• FIG. 2 IF shows, according to some embodiments, corresponding photographs of samples in FIG. 2 IE;
• FIG. 22A shows, according to some embodiments, mass spectroscopy of the headspace gas from a fully-discharged Li-NO2-Ph-SFs cell
• FIG. 22B shows, according to some embodiments, gas chromatography of the headspace gas from a fully-discharged Li-NO2-Ph-SFs cell
• FIG. 22C shows, according to some embodiments, a galvanostatic discharge profile of a Li-NO2-Ph-SFs cell with the corresponding cell pressure
• FIG. 23A shows, according to some embodiments, a galvanostatic discharge profile of Li-NO2-Ph-SFs cells as a function of NO2-PI1-SF5 concentration at 40 pA-cm’ 2 ;
• FIG. 23B shows, according to some embodiments, SEM images of carbon cathodes fully discharged with 3 M NO2-PI1-SF5 / 0.2 M LiC104 / DMSO cathode/electrolyte at 0.3 mA'cm' 2 ;
• FIG. 23C shows, according to some embodiments, theoretical and attained capacities and attained gravimetric energies of Li-NCh-Ph-SFs cells as a function of catholyte concentration;
• FIG. 23D shows, according to some embodiments, the rate capability of cells with 4 M NO2-PI1-SF5 / 0.2 M LiC10 4 / DMSO;
• FIG. 24 shows, according to some embodiments, the ionic conductivity of NO2-PI1- SFs-containing electrolytes as a function of NO2-PI1-SF5 concentration at 50 °C and at RT;
• FIG. 25 shows, according to some embodiments, shelf-life tests for Li-NO2-Ph-SFs cells with 4 M NO2-PI1-SF5 / 0.2 M LiC10 4 / DMSO;
• FIG. 26A shows, according to some embodiments, the weight breakdown of cell components in Li-CF X , Li-NO2-Ph-SFs, and hybrid cells;
• FIG. 26B shows, according to some embodiments, a Ragone plot comparing rate performance of Li-CF X , Li-NO2-Ph-SFs, and hybrid cells;
• FIG. 26C shows, according to some embodiments, the rate performance of hybrid cells using CF X as solid cathode and 4 M NO2-PI1-SF5 / 0.2 M LiC10 4 / DMSO as catholyte;
• FIG. 26D shows, according to some embodiments, SEM images of discharged cathodes from Li-NO2-Ph-SFs cells, hybrid cells, and Li-CF X cells;
• FIG. 27 shows, according to some embodiments, a projection of the theoretical capacity of hybrid cells with different weight ratios
• FIG. 28 shows, according to some embodiments, galvanostatic cycle profiles of Li-NO2-Ph-SFs cell with EC/DMC (left) and DMSO (right) catholyte solvents at 0.04 mA/cm 2 (for cycle) between 1.5-4.6 and 1.9-3.9 V vs. Li/Li + , respectively;
• FIG. 29A shows, according to some embodiments, galvanostatic discharge profiles of Na-NO 2 -Ph-SF 5 cells with 4 M NO2-PI1-SF5 / 0.2 M NaTFSI catholyte in DMSO and EC/PC;
• FIG. 29B shows, according to some embodiments, SEM images of the discharged cathode substrate from the EC/PC -containing cell from FIG. 29A;
• FIG. 30 shows, according to some embodiments, galvanostatic cycle profiles of Na-NO 2 -Ph-SF 5 cell with 0.1 M NO2-PI1-SF5 / 0.2 M NaTFSI in EC/DMC as catholyte and KB as cathode substrate at 0.02 mA/cm 2 between 1.2-4.5 V vs. Na/Na + ; and
• FIG. 31 shows, according to some embodiments, a galvanostatic discharge profile of a Ca-NO 2 -Ph-SF 5 cell with 4 M NO2-PI1-SF5 / 0.2 M CaTFSI in DMSO as catholyte and carbon foam as cathode substrate at 0.04 mA/cm 2 and 50 °C.
• an electrochemical cell described herein comprises 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.
• the halogenated compound comprises a haloalkane (e.g., fluoroalkane) associated with a conjugated system via at least one alkene linker or alkyne linker.
• the halogenated compound comprises a sulfur pentahalide (e.g., pentafluoride) group associated with a conjugated system comprising at least one substituted aromatic group.
• the halogenated compound may be dissolved in an electrolyte solvent and/or 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 complete (or nearly complete) dehalogenation of the molecule.
• halogenated compounds comprising a -CeX 13 haloalkane functional group or a -CsXn haloalkane functional group may be reduced by 11 or 15 electrons, respectively, wherein X is a halogen, such a fluorine, chlorine, bromide, and/or iodide.
• the halogenated compound therefore functions as a catholyte, in some embodiments, such that reduction of the halogenated compound provides electrochemical cells (e.g., batteries) with increased energies and capacities as compared to electrochemical cells that are otherwise equivalent but do not comprise the halogenated compound.
• the electrochemical cells comprising a halogenated compound as described herein provide significant advantages over conventional electrochemical systems.
• Conventional commercialized primary batteries for example, such as Li-SOCh and Li-CF X batteries, deliver good electrochemical performance, but face various challenges.
• Li-SOCh primary batteries for example, deliver high cell-level energy densities (e.g., 480-590 Wh/kg or 950-1100 Wh/L), but utilize liquid SOCh as both cathode and electrolyte, which is highly toxic and corrosive, making such batteries unsuitable for civil applications and/or transportation.
• Li-CF X batteries have a high theoretical specific energy (e.g., 2180 Wh/kg), but the CF X particles are highly insulating, thus the Li-CF X batteries are only suitable for low- to-medium rate applications (e.g., 250-800 Wh/kg or 560-1160 Wh/L).
• Li-fluorinated gas batteries such as Li-SFf, and Li-NFs batteries, may be used for defluorination of fluorinated compounds in a single electrochemical cell setup at RT.
• the large degrees of defluorination enable estimation of the theoretical energy density, which is exceedingly high for gas reactants (e.g., 3900-5100 Wh/kg re actant).
• gas reactants e.g., 3900-5100 Wh/kg re actant
• the limited kinetics and low solubilities (e.g., less than 5 mM) achieved by the dissolved gas nature of the SF 6 and NF3 cathodes results in large overpotentials during cell discharge, which severely hinders the attainable energy densities of these systems.
• the electrochemical cells described herein exhibit high energy densities and capacities.
• the close-to-full dehalogenation of the halogenated compounds can be achieved at practical discharge conditions (e.g., 0.3 mA/cm 2 ), yielding between 8 to 15 e- transfers per molecule and relatively high discharge potentials (e.g., ⁇ 2.6 V).
• high achievable specific energies e.g., up to 2565 Wh/kg re actant
• total capacities e.g., up to 1140 mAh/greactant
• halogenated compounds Furthermore, by tuning the molecular structure of the halogenated compounds, a high degree of electrolyte solubility (e.g., less than or equal to 6 M) is observed, therefore reducing overpotentials arising from the low concentrations in existing metal-gas batteries, making the electrochemical cells described herein comparable to conventional systems, such as Li-CFx primary batteries.
• the structure of the halogenated compounds additionally allows for multiple types of modification (e.g., ring structure, substituent type and position, haloalkene chain length, halogenated group species), which can directly affect the reduction of these molecules. This characteristic not only provides more opportunity for electrochemical performance improvement, but also serves as a new platform to investigate the reduction of halogen-containing molecules.
• FIG. 1A shows a schematic diagram of electrochemical cell 10.
• electrochemical cell 10 comprises a first electrode 12 (e.g., an anode).
• first electrode 12 is or comprises metal 14 (represented by M°, wherein M is a neutral metal atom).
• the metal has a standard reduction potential of less than or equal to about -1.4 V versus the standard hydrogen electrode (SHE).
• the metal may, in certain embodiments, be an alkali metal and/or an alkaline earth metal.
• alkali metals include lithium (Li), sodium (Na), and/or potassium (K).
• alkaline earth metals include magnesium (Mg) and/or calcium (Ca).
• electrochemical cell 10 comprises first electrode 12 (e.g., anode) comprising metal 14, wherein metal 14 is Li. Other metals are also possible.
• first electrode 12 e.g., anode
• metal 14 e.g., alkali metal
• metal 14 is another component of the electrochemical cell other than (or in addition to) the anode, or is in another area of the electrochemical cell.
• the metal may be suspended, dispersed, or dissolved in electrolyte 26 (e.g., electrolyte solution).
• electrochemical cell 10 may comprise second electrode 16 (e.g., cathode).
• second electrode 16 e.g., cathode
• first electrode 12 and second electrode 16 may be in ionic communication with each other, such that ions may move from first electrode 12 to second electrode 16 and vice versa.
• first electrode 12 and second electrode 16 may be mechanically and/or electrically isolated from one another (e.g., in separate containers, by use of a separator, etc.).
• the second electrode may comprise any of a variety of suitable materials.
• the second electrode comprises carbon and/or a metal.
• the second electrode comprises graphite, graphene, graphene oxide, a carbon nanomaterial (e.g., carbon nanotubes, carbon nanofibers), carbon powder (e.g., Vulcan carbon, carbon black, and the like), and/or a carbon gas diffusion layer (GDL).
• electrochemical cell 10 comprising second electrode 16 e.g., cathode
• comprises carbon e.g., carbon black).
• the second electrode comprises a carbonized material.
• the term “carbonized material” generally refers to a carbon-containing composition that is heated under a controlled atmosphere that allows for partial oxidation and formation of extended conjugation. Carbonized materials may, in some embodiments, comprise elements other than carbon, provided those elements were 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 can include are metals (e.g., tin), nitrogen, phosphorous, oxygen, and/or silicon.
• the second electrode comprises CF X .
• CF X CF X .
• use of a cathode comprising CF X in combination with a halogenated compound in an electrochemical cell may provide an enhanced electrochemical performance, such as an increased specific energy.
• the second electrode may, in some embodiments, comprise platinum (Pt), nickel (Ni), palladium (Pd), iron (Fe), cobalt (Co), gold (Au), and/or copper (Cu).
• the second electrode may comprise a metal oxide (e.g., manganese oxide (MnO) or nickel oxide (NiO)), a metal sulfide, and/or a metal fluoride. Other materials are also possible.
• electrochemical cell including anode active materials, cathode active materials, electrolytes, and the like are described herein in further detail.
• the second electrode may comprise a halogenation layer.
• the electrochemical cell may comprise the first electrode and/or the second electrode in any of a variety of suitable mass loadings.
• the electrochemical cell comprises the first electrode and/or the second electrode with a mass loading greater than or equal to 0.1 mg/cm 2 , greater than or equal to 1 mg/cm 2 , greater than or equal to 5 mg/cm 2 , greater than or equal to 10 mg/cm 2 , greater than or equal to 20 mg/cm 2 , greater than or equal to 30 mg/cm 2 , greater than or equal to 40 mg/cm 2 , greater than or equal to 50 mg/cm 2 , greater than or equal to 60 mg/cm 2 , greater than or equal to 70 mg/cm 2 , greater than or equal to 80 mg/cm 2 , greater than or equal to 90 mg/cm 2 , greater than or equal to 100 mg/cm 2 , greater than or equal to 120 mg/cm 2 , greater than or equal to 140 mg/cm 2 , greater than or equal to
• the electrochemical cell comprises the first electrode and/or the second electrode with a mass loading less than or equal to 200 mg/cm 2 , less than or equal to 180 mg/cm 2 , less than or equal to 160 mg/cm 2 , less than or equal to 140 mg/cm 2 , less than or equal to 120 mg/cm 2 , less than or equal to 100 mg/cm 2 , less than or equal to 90 mg/cm 2 , less than or equal to 80 mg/cm 2 , less than or equal to 70 mg/cm 2 , less than or equal to 60 mg/cm 2 , less than or equal to 50 mg/cm 2 , less than or equal to 40 mg/cm 2 , less than or equal to 30 mg/cm 2 , less than or equal to 20 mg/cm 2 , less than or equal to 10 mg/cm 2 , less than or equal to 5 mg/cm 2 , less than or equal to 1 mg/cm 2 , or less.
• the electrochemical cell comprises the first electrode and/or the second electrode with a mass loading between greater than or equal to 0.1 mg/cm 2 and less than or equal to 200 mg/cm 2
• the electrochemical cell comprises the first electrode and/or the second electrode with a mass loading between greater than or equal to 30 mg/cm 2 and less than or equal to 70 mg/cm 2 ).
• Other ranges are also possible.
• the electrochemical cell comprises a halogenated compound.
• halogenated compound refers to an individual molecules of the halogenated compound.
• electrochemical cell 10 comprises halogenated compound 11.
• Halogenated compound 11 in FIG. 1A for example, electrochemical cell 10 comprises halogenated compound 11.
• RX 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).
• halogen e.g., a fluorine ion
• 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).
• the halogenated compound comprises a haloalkane.
• haloalkane is given its ordinary meaning in the art and generally refers to a molecule comprising an alkane chain containing one or more halogens.
• the haloalkane comprises a carbon-based skeleton that contains carbon-halogen bonds (e.g., carbon-fluorine bonds).
• the carbon skeleton can be linear, cyclic, branched, and/or optionally substituted (e.g., with one or more different functional groups).
• the haloalkane is of the form CnX2n+i, wherein n is greater than or equal to 1 and each X is the same or a different halogen, such as fluorine, chlorine, bromine, and/or iodine.
• the haloalkane is of the form C n X2n+i, wherein n is greater than or equal to 1 and each X is the same (e.g., fluorine).
• the haloalkane may be a CeXi3 (e.g., CeFn) group or a CsXn (e.g., CsFrz) group.
• the halogenated compound may comprise a mixture of haloalkanes.
• the halogenated compound comprises a mixture of fluoroalkanes, chloroalkanes, bromoalkanes, and/or iodoalkanes.
• the choice of haloalkane depends, in some embodiments, on a number of factors, including cost, solubility, melting point, viscosity, stability prior to electrochemical cell discharge, and discharge efficiency.
• the haloalkane is associated with a conjugated system.
• conjugated system is given its ordinary meaning in the art and generally refers to a molecular system of p-orbitals with delocalized electrons, conventionally represented by alternating single and multiple carbon bonds.
• the conjugated system comprises a contiguous arrangement of at least four carbon atoms having 7t-orbital bonding between them.
• the conjugated system may comprise heteroatoms, such as nitrogen or oxygen atoms, in place of one or more of the carbon atoms, which participate in strong 7t-bonds with carbon atoms.
• the 7t-orbitals in a conjugated system are delocalized and the bonding interactions associated with one orbital are not restricted to be between only two carbons, as is the case for a localized bond, such as a C-C single bond or the 7t-bond in between carbons in ethylene or acetylene.
• the conjugated system comprises at least one optionally substituted aromatic group.
• the aromatic group has a cyclic structure with delocalized 7t-bonding.
• the conjugated system comprises benzene.
• the conjugated system may comprise greater than one optionally substituted aromatic group (e.g., two optionally substituted aromatic groups, three optionally substituted aromatic groups, four optionally substituted aromatic groups, etc.).
• the conjugated system comprises naphthalene, anthracene, pyrene, and/or quinoline.
• the conjugated system comprises greater than one optionally substituted aromatic group
• the aromatic stabilization on a per-ring basis is reduced and the molecules react in a way that produces intermediates that maximize aromatic character, and as a result, the additional optionally substituted aromatic groups behave similar to alkenes in terms of reactivity.
• the haloalkane is associated with the conjugated system via at least one alkene linker or alkyne linker.
• the alkene linker or alkyne linker is part of the conjugated system, in some embodiments, such that the alkene linker or alkyne linker are in conjugation and participate in delocalized bonding with the conjugated system.
• the conjugated system may comprise at least one optionally substituted aromatic group (e.g., benzene) functionalized with an alkene linker or an alkyne linker that creates a linkage to the haloalkane.
• the conjugated system may comprise greater than one optionally substituted aromatic group (e.g., naphthalene) functionalized with an alkene linker or an alkyne linker that creates a linkage to the haloalkane.
• the alkene linker or the alkyne linker is a portion of one or more optionally substituted aromatic groups.
• the conjugated system may comprise greater than one optionally substituted aromatic group and the alkene linker or alkyne linker is associated with one of the optionally substituted aromatic groups.
• FIG. 2 shows, according to some embodiments, a series of non-limiting halogenated compounds, each comprising a haloalkane associated with a conjugated system via at least one alkene linker or alkyne linker.
• Structure A shows, according to certain embodiments, a conjugated system comprising benzene, an alkene linker as part of the conjugated system, and a haloalkane associated with the conjugated system via the alkene linker.
• Structure B shows, according to certain embodiments, a conjugated system comprising benzene, an alkyne linker as part of the conjugated system, and a haloalkane associated with the conjugated system via the alkyne linker.
• Structure C shows, according to certain embodiments, a conjugated system comprising naphthalene, two alkene linkers associated with naphthalene as part of the conjugated system, and a haloalkane associated with the conjugated system via the alkene linkers.
• Structure D shows, according to certain embodiments, a conjugated system comprising anthracene, four alkene linkers associated with anthracene as part of the conjugated system, and a haloalkane associated with the conjugated system via the alkene linkers.
• Structure E shows, according to certain embodiments, a conjugated system comprising quinoline, an alkene linker associated with the quinoline as part of the conjugated system, and a haloalkane associated with the conjugated system via the alkene linker.
• Structure F shows, according to certain embodiments, a conjugated system comprising quinoline, an alkyne linker as part of the conjugated system, and a haloalkane associated with the conjugated system via the alkyne linker.
• Structure G shows, according to certain embodiments, a conjugated system comprising naphthalene, an alkene linker associated with naphthalene as part of the conjugated system, and a haloalkane associated with the conjugated system via the alkene linker.
• Structure H shows, according to certain embodiments, a conjugated system comprising anthracene, two alkene linkers associated with the anthracene as part of the conjugated system, and a haloalkane associated with the conjugated system via the alkene linkers. It should be understood that the structures shown in FIG. 2 are not meant to be limiting, and a person of ordinary skill in the art could envision further halogenated compounds comprising a haloalkane associated with a conjugated system via at least one alkene linker or alkyne linker.
• Ar comprises one optionally substituted aromatic group (e.g., benzene, pyridine).
• Ar comprises more than one optionally substituted aromatic group (e.g., naphthalene).
• the halogenated compound is selected from the group consisting of:
• halogenated compounds comprising a haloalkane associated with a conjugated system via at least one alkene linker or alkyne linker are possible, as the disclosure is not meant to be limiting in this regard.
• the halogenated compound comprises a sulfur pentahalide (e.g., pentafluoride) group associated with a conjugated system.
• the halogenated compound comprises at least one sulfur pentafluoride group associated with the conjugated system.
• the halogenated compound may comprise one sulfur pentafluoride group, two sulfur pentafluoride groups, three sulfur pentafluoride groups, four sulfur pentafluoride groups, or more, associated with the conjugated system.
• the conjugated system may comprise a substituted aromatic group.
• the halogenated compound comprises at least one sulfur pentafluoride group associated with a conjugated system comprising a substituted benzene.
• the substitution of the at least one sulfur pentafluoride group on the aromatic group in the ortho-, para-, or meta- position advantageously affords the halogenated compound with increased solubilities in the electrolyte, as compared to, for example, a halogenated compound that is otherwise equivalent without substitution on the benzene ring.
• the increased solubility of the halogenated compound contributes to increased energy densities associated with the electrochemical system during discharge.
• the halogenated compound is selected from the group consisting of:
• the halogenated compound may be ionic.
• the halogenated compound may comprise a charged (e.g., positively charged, negatively charged) ion.
• 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 the conjugated system.
• the charged ion may be a substituent of the conjugated system.
• the halogenated compound comprises:
• a current and/or voltage is applied to the electrochemical cell.
• the electrochemical may be charged and/or discharged.
• the electrochemical cell may be discharged to any of a variety of suitable capacities.
• the discharge capacity may depend on the components of the electrochemical cell (e.g., the composition of the electrodes and/or the electrolyte, etc.) and/or the amount of the components in the electrochemical cell (e.g., the mass loading of the electrodes and/or the electrolyte, etc.).
• the electrochemical cell is discharged to a capacity (e.g., an areal capacity) greater than or equal to 0.05 mAh/cm 2 , greater than or equal to 1 mAh/cm 2 , greater than or equal to 2 mAh/cm 2 , greater than or equal to 5 mAh/cm 2 , greater than or equal to 10 mAh/cm 2 , greater than or equal to 15 mAh/cm 2 , greater than or equal to 20 mAh/cm 2 , greater than or equal to 25 mAh/cm 2 , greater than or equal to 30 mAh/cm 2 , greater than or equal to 35 mAh/cm 2 , greater than or equal to 40 mAh/cm 2 , greater than or equal to 45 mAh/cm 2 , greater than or equal to 50 mAh/cm 2 , greater than or equal to 55 mAh/cm 2 , or greater.
• a capacity e.g., an areal capacity
• the electrochemical cell is discharged to a capacity less than or equal to 60 mAh/cm 2 , less than or equal to 55 mAh/cm 2 , less than or equal to 50 mAh/cm 2 , less than or equal to 45 mAh/cm 2 , less than or equal to 40 mAh/cm 2 , less than or equal to 35 mAh/cm 2 , less than or equal to 30 mAh/cm 2 , less than or equal to 25 mAh/cm 2 , less than or equal to 20 mAh/cm 2 , less than or equal to 15 mAh/cm 2 , less than or equal to 10 mAh/cm 2 , less than or equal to 5 mAh/cm 2 , less than or equal to 2 mAh/cm 2 , less than or equal to 1 mAh/cm 2 , or less.
• the electrochemical cell is discharged to a capacity between greater than or equal to 0.05 mAh/cm 2 and less than or equal to 60 mAh/cm 2
• the electrochemical cell is discharged to a capacity between greater than or equal to 10 mAh/cm 2 and less than or equal to 15 mAh/cm 2
• Other ranges are also possible.
• the areal capacity of the electrochemical cell may depend on the contents of the electrochemical cell, including, for example, the electrode materials and their mass loadings, the electrolyte material and volume, and/or the choice of halogenated compound and its concentration, and therefore may be tailored depending on how the electrochemical cell is engineered.
• the electrochemical cell is fully discharged.
• the term “fully discharged” generally means that the electrochemical cell is discharged until the theoretical capacity of the halogenated compound is reached or the theoretical capacity of the halogenated compound is not reached but cathode passivation (e.g., by LiF) leads to electrochemical cell termination.
• the electrochemical cell may be discharged at any of a variety of suitable current densities.
• the discharge capacity may depend on the specific components of the electrochemical cell (e.g., the composition of the electrodes and/or the electrolyte) and/or the amount of the components in the electrochemical cell (e.g., the mass loading of the electrodes and/or the electrolyte, etc.).
• the electrochemical cell is discharged at a current density greater than or equal to 1 microampere/cm 2 , greater than or equal to 500 microamperes/cm 2 , greater than or equal to 1 milliamperes/cm 2 , greater than or equal to 2 milliamperes/cm 2 , greater than or equal to 3 milliamperes/cm 2 , greater than or equal to 4 milliamperes/cm 2 , greater than or equal to 5 milliamperes/cm 2 , greater than or equal to 6 milliamperes/cm 2 , greater than or equal to 7 milliamperes/cm 2 , greater than or equal to 8 milliamperes/cm 2 , greater than or equal to 9 milliamperes/cm 2 , or greater.
• the electrochemical cell is discharged at a current density less than or equal to 10 milliamperes/cm 2 , less than or equal to 9 milliamperes/cm 2 , less than or equal to 8 milliamperes/cm 2 , less than or equal to 7 milliamperes/cm 2 , less than or equal to 6 milliamperes/cm 2 , less than or equal to 5 milliamperes/cm 2 , less than or equal to 4 milliamperes/cm 2 , less than or equal to 3 milliamperes/cm 2 , less than or equal to 2 milliamperes/cm 2 , less than or equal to 1 milliamperes/cm 2 , less than or equal to 500 microamperes/cm 2 , or less.
• the electrochemical cell is discharged at a current density between greater than or equal to 1 microampere/cm 2 and less than or equal to 10 milliamperes/cm 2
• the electrochemical cell is discharged at a current density between greater than or equal to 4 milliamperes/cm 2 and less than or equal to 6 milliamperes/cm 2 ).
• Other ranges are also possible.
• the electrochemical cell is discharged at a current density greater than or equal to 50 mA/gc, greater than or equal to 500 mA/gc, greater than or equal to 1 A/gc, greater than or equal to 2 A/gc, greater than or equal to 3 A/gc, greater than or equal to 4 A/gc, greater than or equal to 5 A/gc, greater than or equal to 6 A/gc, greater than 7 A/gc, greater than 8 A/gc, greater than 9 A/gc, or greater.
• the electrochemical cell is discharged at a current density less than or equal to 10 A/gc, less than or equal to 9 A/gc, less than or equal to 8 A/gc, less than or equal to 7 A/gc, less than or equal to 6 A/gc, less than or equal to 5 A/gc, less than or equal to 4 A/gc, less than or equal to 3 A/gc, less than or equal to 2 A/gc, less than or equal to 1 A/gc, less than or equal to 500 mA/gc, or less.
• the electrochemical cell is discharged at a current density between greater than or equal to 50 mA/gc and less than or equal to 10 A/gc, the electrochemical cell is discharged at a current density between greater than or equal to 1 A/gc and less than or equal to 5 A/gc).
• Other ranges are also possible.
• the electrochemical cell may be discharged (and/or charged) at any of a variety of suitable temperatures.
• the electrochemical cell is discharged (and/or charged) at a temperature that is greater than the freezing point of the electrolyte solvent.
• the electrochemical cell is discharged (and/or charged) at a temperature greater than or equal to 10 °C, greater than or equal to 20 °C, greater than or equal to 30 °C, greater than or equal to 40 °C, greater than or equal to 50 °C, greater than or equal to 60 °C, greater than or equal to 70 °C, or greater.
• the electrochemical cell is discharged (and/or charged) at a temperature less than or equal to 80 °C, less than or equal to 70 °C, less than or equal to 60 °C, less than or equal to 50 °C, less than or equal to 40 °C, less than or equal to 30 °C, less than or equal to 20 °C, less than or equal to 0 °C, or less.
• the electrochemical cell is discharged and/or charged at a temperature between greater than or equal to 10 °C and less than or equal to 80 °C, the electrochemical cell is discharged and/or charged at a temperature between greater than or equal to 20 °C and less than or equal to 30 °C).
• the electrochemical cell is discharged (and/or charged) at RT (e.g., between 20-22 °C)
• a method of discharging an electrochemical cell comprises oxidizing at least a portion of the alkali metal and/or the alkaline earth metal, thereby providing an alkali metal ion and/or an alkaline earth metal ion.
• FIG. IB shows, according to some embodiments, a schematic diagram of an electrochemical cell comprising an alkali metal ion and/or an alkaline earth metal ion. As shown in FIG.
• electrochemical cell 10 may be discharged (e.g., at any of a variety of suitable current densities), thereby providing electrons 8 from first electrode 12 (e.g., anode) comprising metal 14 (e.g., alkali metal and/or alkaline earth metal).
• first electrode 12 e.g., anode
• metal 14 e.g., alkali metal and/or alkaline earth metal
• metal ion 18 e.g., alkali metal ion.
• IB is represented by the formula M + , wherein 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.
• metal ion 18 is suspended, dispersed, and/or dissolved in electrolyte 26 (e.g., electrolyte solution).
• discharging comprises reducing at least a portion of the halogenated compound, thereby providing a reduced halogenated compound.
• the reduced halogenated compound may, in some embodiments, comprise a fragment.
• the reduced halogenated compound comprises a charged species, a neutral species, or a radical.
• 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.
• the atom that is converted from a first oxidation state to a second oxidation state is a halogenated atom.
• halogenated atom refers to an atom that is bound (e.g., covalently, non-covalently) to one or more halogen atoms, such as, for example, a carbon atom or a sulfur atom. The reduced halogenated compound is explained in greater detail herein.
• the halogenated compound is capable of being reduced by a high number of electrons.
• the description of a compound (e.g., a halogenated compound) capable of being reduced by electrons as used herein generally refers to the ability of the compound to gain electrons in a reduction reaction as a result of an oxidation-reduction electron transfer process.
• the halogenated compound is reduced by greater than or equal to two electrons, greater than or equal to four electrons, greater than or equal to six electrons, greater than or equal to eight electrons, greater than or equal to ten electrons, greater than or equal to eleven electrons, greater than or equal to twelve electrons, greater than or equal to fourteen electrons, greater than or equal to fifteen electrons, greater than or equal to sixteen electrons, greater than or equal to eighteen electrons, or more.
• the halogenated compound is reduced by less than or equal to twenty electrons, less than or equal to eighteen electrons, less than or equal to sixteen electrons, less than or equal to fifteen electrons, less than or equal to fourteen electrons, less than or equal to twelve electrons, less than or equal to eleven electrons, less than or equal to ten electrons, less than or equal to eight electrons, less than or equal to six electrons, less than or equal to four electrons, less than or equal to two electrons, or less.
• the halogenated compound is reduced by between greater than or equal to two electrons and less than or equal to twenty electrons, the halogenated compound is reduced by between greater than or equal to twelve electrons and less than or equal to sixteen electrons).
• Other ranges are also possible.
• the halogenated compound comprises a haloalkane associated with a conjugated system via at least one alkene linker or alkyne linker, and the halogenated compound is capable of being reduced by greater than or equal to six electrons, greater than or equal to eight electrons, greater than or equal to ten electrons, greater than or equal to twelve electrons, or greater than or equal to fourteen electrons.
• the halogenated compound comprises a haloalkane associated with a conjugated system via at least one alkene linker or alkyne linker, and the halogenated compound is capable of being reduced by less than or equal to sixteen electrons, less than or equal to fourteen electrons, less than or equal to twelve electrons, less than or equal to ten electrons, or less than or equal to eight electrons.
• the halogenated compound comprises a haloalkane associated with a conjugated system via at least one alkene linker or alkyne linker, and the halogenated compound is capable of being reduced by between greater than or equal to six electrons and less than or equal to fourteen electrons).
• Other ranges are also possible.
• the halogenated compound comprises a sulfur pentafluoride group associated with a conjugated system comprising at least one substituted aromatic group, and the halogenated compound is capable of being reduced by greater than or equal to two electrons, greater than or equal to four electrons, greater than or equal to six electrons, greater than or equal to eight electrons, or greater than or equal to ten electrons.
• the halogenated compound comprises a sulfur pentafluoride group associated with a conjugated system comprising at least one substituted aromatic group, and the halogenated compound is capable of being reduced by less than or equal to twelve electrons, less than or equal to ten electrons, less than or equal to eight electrons, less than or equal to six electrons, or less than or equal to four electrons. Combinations of the above recited ranges are also possible (e.g., the halogenated compound comprises a sulfur pentafluoride group associated with a conjugated system comprising at least one substituted aromatic group, and the halogenated compound is capable of being reduced by between greater than or equal to two electrons and less than or equal to twelve electrons). Other ranges are also possible.
• the number of electrons that the halogenated compound is reduced by may be determined by techniques known to a person of ordinary skill in the art.
• the halogenated compound comprises a haloalkane associated with a conjugated system via at least one an alkene linker or alkyne linker, wherein x is the number of halogen atoms on the haloalkane, and the halogenated compound is reduced by up to x-2 electrons.
• the halogenated compound comprises at least one sulfur pentafluoride group associated with a conjugated system, wherein the number of fluorine atoms is x, the number of sulfur atoms is y, and the conjugated system is z.
• the halogenated compound may be reduced by up to x+2y+z electrons.
• the halogenated compound comprises at least one sulfur pentafluoride group associated with a conjugated system and at least one substituent (e.g., NO2 group) associated with the conjugated system, wherein 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.
• the halogenated compound may be reduced by up to x+2y+y’+z electrons.
• conversion of the halogenated atom from the first oxidation state to the second oxidation state results in the removal of one or more halogen atoms (e.g., two or more halogen atoms, four or more halogen atoms, six or more halogen atoms, eight or more halogen atoms, ten or more halogen atoms, twelve or more halogen atoms, all halogen atoms) bound (e.g., covalently bound, non-covalently bound) to the halogenated atom.
• one or more halogen atoms e.g., two or more halogen atoms, four or more halogen atoms, six or more halogen atoms, eight or more halogen atoms, ten or more halogen atoms, twelve or more halogen atoms, all halogen atoms
• the change in oxidation state of the one or more halogenated atoms may result in the cleavage of one or more halogenated atom-halogen bonds (e.g., two or more cleavages, four or more cleavages, six or more cleavages, eight or more cleavages, ten or more cleavages, twelve or more cleavages, cleavage of all halogenated atom-halogen bonds).
• the change in oxidation state results in the conversion of the halogenated atom to a reduced, non-halogenated atom.
• cleavage of one or more halogenated atom-halogen bonds may result in the formation of one or more halide ions.
• the cleavage of one or more halogenated atom-halogen bonds may result in the formation of one or more fluoride (F ) ions, which is explained herein in greater detail.
• the halogenated atom-halogen bonds may be carbon-halo (e.g., carbon-fluoro) bonds.
• discharging comprises reducing greater than or equal to 50% of the carbon-halo bonds of the halogenated compound, greater than or equal to 60% of the carbon-halo bonds of the halogenated compound, greater than or equal to 70% of the carbon-halo bonds of the halogenated compound, greater than or equal to 80% of the carbon-halo bonds of the halogenated compound, greater than or equal to 90% of the carbon-halo bonds of the halogenated compound, or greater.
• discharging comprises 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.
• discharging comprises reducing between greater 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
• discharging comprises reducing between greater 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).
• the halogenated atom-halogen bonds may be sulfur-halo (e.g., sulfur-fluoro) bonds.
• discharging comprises reducing greater than or equal to 50% of the sulfur-halo bonds of the halogenated compound, greater than or equal to 60% of the sulfur-halo bonds of the halogenated compound, greater than or equal to 70% of the sulfur-halo bonds of the halogenated compound, greater than or equal to 80% of the sulfur-halo bonds of the halogenated compound, greater than or equal to 90% of the sulfur-halo bonds of the halogenated compound, or greater.
• discharging comprises 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 sulfur-halo bonds of the halogenated compound, or less.
• discharging comprises reducing between greater 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
• discharging comprises reducing between greater 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.
• incorporación of the halogenated compound in the electrochemical cell may advantageously provide a system with a higher specific energy as compared to an electrochemical system that is otherwise equivalent but does not comprise the halogenated compound.
• the specific energy of the electrochemical cell may be greater than or equal to 600 Wh/kg re actant, greater than or equal to 800 Wh/kgreactant, greater than or equal to 1000 Wh/kg re actant, greater than or equal to 1200
• Wh/kgreactant greater than or equal to 1400 Wh/kg re actant, greater than or equal to 1600
• Wh/kgreactant greater than or equal to 1800 Wh/kgreactant, greater than or equal to 2000
• Wh/kgreactant greater than or equal to 2200 Wh/kg re actant, greater than or equal to 2400
• the specific energy of the electrochemical cell is less than or equal to 3000 Wh/kg re actant, less than or equal to 2800 Wh/kg re actant, less than or equal to 2600 Wh/kg re actant, less than or equal to 2400 Wh/kgreactant, less than or equal to 2200 Wh/kg re actant, less than or equal to 2000 Wh/kgreactam, less than or equal to 1800 Wh/kg re actant, less than or equal to 1600 Wh/kg re actant, less than or equal to 1400 Wh/kg re actant, less than or equal to 1200 Wh/kg re actant, less than or equal to 1000 Wh/kg re actant, or less than or equal to 800 Wh/kg re actant, wherein
• the specific energy of the electrochemical cell is between greater than or equal to 600 Wh/kgreactant and less than or equal to 3000 Wh/kg re actant, wherein the reactant is the halogenated compound
• the specific energy of the electrochemical cell is between greater than or equal to 1800 Wh/kg re actant and less than or equal to 2200 Wh/kg re actant, wherein the reactant is the halogenated compound.
• Other ranges are also possible.
• the specific energy of the electrochemical cell is greater than or equal to 600 Wh/kg re actant, greater than or equal to 800 Wh/kg re actant, greater than or equal to 1000 Wh/kg re actant, greater than or equal to 1200 Wh/kg re actant, greater than or equal to 1400 Wh/kg re actant, greater than or equal to 1600 Wh/kgreactant, or greater than or equal to 1800 Wh/kg re actant, wherein the reactant is the halogenated compound.
• the specific energy of the electrochemical cell is less than or equal to 2000 Wh/kgreactant, leSS than or equal to 1800 Wh/kgreactant, less than or equal to 1600 Wh/kgreactant, less than or equal to 1400 Wh/kg re actant, less than or equal to 1200 Wh/kg re actant, less than or equal to 1000 Wh/kg re actant, or less than or equal to 800 Wh/kg re actant, wherein the reactant is the halogenated compound.
• the halogenated compound comprises a haloalkane associated with a conjugated system via at least one alkene linker or alkyne linker and the specific energy of the electrochemical cell is between greater than or equal to 600 Wh/kg re actant and less than or equal to 2000 Wh/kgreactant, wherein the reactant is the halogenated compound).
• the halogenated compound comprises a haloalkane associated with a conjugated system via at least one alkene linker or alkyne linker and the specific energy of the electrochemical cell is between greater than or equal to 600 Wh/kg re actant and less than or equal to 2000 Wh/kgreactant, wherein the reactant is the halogenated compound).
• Other ranges are also possible.
• the specific energy of the electrochemical cell is greater than or equal to 1000 Wh/kg re actant, greater than or equal to 1200 Wh/kg re actant, greater than or equal to 1400 Wh/kgreactant, greater than or equal to 1600 Wh/kg re actant, greater than or equal to 1800 Wh/kgreactant, greater than or equal to 2000 Wh/kg re actant, greater than or equal to 2200 Wh/kgreactant, greater than or equal to 2400 Wh/kg re actant, or greater than or equal to 2600 Wh/kgreactant, wherein the reactant is the halogenated compound.
• the specific energy of the electrochemical cell is less than or equal to 2800 Wh/kg re actant, less than or equal to 2600 Wh/kgreactant, less than or equal to 2400 Wh/kg re actant, less than or equal to 2200 Wh/kg re actant, less than or equal to 2000 Wh/kg re actant, less than or equal to 1800 Wh/kg re actant, less than or equal to 1600 Wh/kg re actant, or less than or equal to 1400 Wh/kg re actant, wherein the reactant is the halogenated compound.
• the halogenated compound comprises a sulfur pentafluoride group associated with a conjugated system comprising at least one substituted aromatic group and the specific energy of the electrochemical cell is between greater than or equal to 1000 Wh/kg re actant and less than or equal to 2800 Wh/kg re actant, wherein the reactant is a halogenated compound).
• the reactant is a halogenated compound.
• Other ranges are also possible.
• a solid-liquid hybrid electrochemical cell comprising a solid anode, a solid cathode, and a liquid electrolyte, wherein the liquid electrolyte comprises the halogenated compound and the solid cathode comprises a high-capacity material that is voltage-matched with the halogenated compound.
• the solid cathode may comprise CF X or MnCh.
• the attainable specific energy of the electrochemical cell may be relatively high.
• the cathodic discharge of the high- capacity, voltage-matched cathode (e.g., comprising CF X or MnCh) and the halogenated compound may, for example, provide a relatively high specific energy as compared to: (i) an electrochemical cell that is otherwise equivalent but does not comprise the high-capacity, voltage-matched cathode or the halogenated compound; (ii) an electrochemical cell that is otherwise equivalent but does not comprise the high-capacity, voltage-matched cathode; or (iii) an electrochemical cell that is otherwise equivalent but does not comprise the halogenated compound.
• incorporation of the halogenated compound in the electrochemical cell may advantageously provide a system with a higher total capacity as compared to an electrochemical system that is otherwise equivalent but does not comprise the halogenated compound.
• the total capacity of the electrochemical cell may be greater than or equal to 200 mAh/greactant, greater than or equal to 400 mAh/greactant, greater than or equal to 600 mAh/greactant, greater than or equal to 800 mAh/greactant, greater than or equal to 1000 mAh/greactant, or greater than or equal to 1200 mAh/greactant, wherein the reactant is the halogenated compound.
• the total capacity of the electrochemical cell may be less than or equal to 1400 mAh/greactant, less than or equal to 1200 mAh/greactant, less than or equal to 1000 mAh/greactant, less than or equal to 800 mAh/greactant, less than or equal to 600 mAh/greactant, or less than or equal to 400 mAh/greactant, wherein the reactant is the halogenated compound.
• the total capacity of the electrochemical cell is greater than or equal to 200 mAh/greactant and less than or equal to 1400 mAh/greactant, the total capacity of the electrochemical cell is greater than or equal to 800 mAh/greactant and less than or equal to 1000 mAh/g reactant ).
• Other ranges are also possible.
• the total capacity of the electrochemical cell is greater than or equal to 200 mAh/greactant, greater than or equal to 400 mAh/greactant, greater than or equal to 600 mAh/greactant, greater than or equal to 800 mAh/greactant, or greater than or equal to 1000 mAh/greactant, wherein the reactant is the halogenated compound.
• the total capacity of the electrochemical cell is less than or equal to 1200 mAh/greactant, less than or equal to 1000 mAh/greactant, less than or equal to 800 mAh/greactant, less than or equal to 600 mAh/greactant, or less than or equal to 400 mAh/greactant, wherein the reactant is the halogenated compound.
• the halogenated compound comprises a haloalkane associated with a conjugated system via at least one alkene linker or alkyne linker and the total capacity of the electrochemical cell is between greater than or equal to 200 mAh/greactant and less than or equal to 1200 mAh/greactant, wherein the reactant is the halogenated compound).
• the halogenated compound comprises a haloalkane associated with a conjugated system via at least one alkene linker or alkyne linker and the total capacity of the electrochemical cell is between greater than or equal to 200 mAh/greactant and less than or equal to 1200 mAh/greactant, wherein the reactant is the halogenated compound).
• Other ranges are also possible.
• the total capacity of the electrochemical cell is greater than or equal to 200 mAh/greactant, greater than or equal to 400 mAh/greactant, greater than or equal to 600 mAh/greactant, greater than or equal to 800 mAh/greactant, greater than or equal to 1000 mAh/greactant, or greater than or equal to 1200 mAh/greactant, wherein the reactant is the halogenated compound.
• the total capacity of the electrochemical cell is less than or equal to 1400 mAh/greactant, less than or equal to 1200 mAh/greactant, less than or equal to 1000 mAh/greactant, less than or equal to 800 mAh/greactant, less than or equal to 600 mAh/greactant, or less than or equal to 400 mAh/greactant, wherein the reactant is the halogenated compound.
• the halogenated compound comprises a sulfur pentafluoride group associated with a conjugated system comprising at least one substituted aromatic group and the total capacity of the electrochemical cell is between greater than or equal to 200 mAh/greactant and less than or equal to 1400 mAh/greactant, wherein the reactant is a halogenated compound).
• the reactant is a halogenated compound.
• Other ranges are also possible.
• FIG. 1C shows, according to some embodiments, a schematic diagram of an electrochemical cell comprising a reduced halogenated compound.
• electrochemical cell 10 may be discharged (e.g., at any of a variety of suitable current densities), thereby providing electrons 8 from first electrode 12 (e.g., anode).
• first electrode 12 e.g., anode
• halogenated compound 11 is reduced, thereby providing a reduced halogenated compound.
• the reduced halogenated compound may comprise one or more reduced products 22 (e.g., a reduced, non-halogenated atom) and one or more halide ions 20. Reduced product 22 in FIG.
• 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).
• R’ may be a charged species, a neutral species, or a radical.
• Halide ion 20 is represented by X’, where X is a halide ion (e.g., an anionic fluorine) in a reduced (e.g., -1) oxidation state.
• reduced product 22 and/or halide ion 20 resulting from the reduction of the halogenated compound may be dissolved in electrolyte 26 (e.g., electrolyte solution).
• oxidizing at least a portion of the alkali metal and/or the alkaline earth metal provides an alkali metal ion and/or an alkaline earth metal ion
• reducing at least a portion of the halogenated compound provides a reduced halogenated compound (e.g., one or more reduced products and one or more halide ions).
• the method may further comprise reacting the alkali metal ion and/or the alkaline earth metal ion with the one or more halide ions to form a halogenation layer on at least a portion of the second electrode.
• the halogenation layer may, in certain embodiments, comprise a metal salt (e.g., an alkali metal salt, an alkaline earth metal salt).
• the reaction product comprising the metal salt deposits on the substrate (e.g., on a surface of the substrate) to form the halogenation layer.
• FIG. ID shows, according to some embodiments, a schematic diagram of an electrochemical cell comprising a halogenation layer.
• second electrode 16 e.g., cathode
• second electrode 16 (e.g., cathode) comprises halogenation layer 28 comprising metal salt 24, wherein metal salt 24 is LiF.
• the metal that reacts with one or more halide ions may be selected such that the reaction between the metal and the one or more halide ions is an exergonic reaction. Without being bound by theory, it is believed that the exergonic reaction facilitates the electrochemical reaction and minimizes the presence of potential hazardous reaction products and/or contaminants within the halogenation layer.
• the reaction between the alkali metal ion and/or the alkaline earth metal ion and the halide ion occurs at or near an electrified interface in an electrochemical cell.
• the term “electrified interface” generally refers to the interface between two dissimilar materials in which an interfacial potential difference exists.
• the electrified interface may be the interface between a first material (e.g., an electrode) and a second material that has a different composition than the first material (e.g., an electrolyte).
• the reaction between the oxidized alkali metal ion and the reduced halogenated compound occurs at the electrified interface between the substrate (e.g., cathode) and the electrolyte (e.g., electrolyte solution).
• the reaction between the alkali metal ion and/or the alkaline earth metal ion and the halide ion may occur at electrified interface 29 between second electrode 16 (e.g., cathode) and electrolyte 26 (e.g., electrolyte solution).
• At least a portion of the reaction product comprising metal salt 24 deposits on second electrode 16 (e.g., cathode) as halogenation layer 28.
• the reaction between the alkali metal ion and/or the alkaline earth metal ion and the halide ion occurring at electrified interface 29 may provide a high concentration of the reaction product comprising metal salt 24 at electrified interface 29.
• electrified interface 29 e.g., between second electrode 16 and electrolyte 26
• the halogenation layer may, in certain embodiments, act as a passivation layer that protects the substrate that it is disposed on from deterioration and/or decay that may be caused by external forces (e.g., a solvent and/or electrolyte of an electrochemical cell).
• the halogenation layer is configured to protect at least a portion of the substrate (e.g., electrode) from corrosion. Corrosion of a substrate (e.g., electrode) is caused, in some cases, by cycling an electrochemical cell comprising the substrate, therefore causing subsequent reactivity between the substrate and the solvent and/or electrolyte of the electrochemical cell.
• the halogenation layer may provide a reservoir of halide ions (e.g., fluoride ions).
• the halogenation layer may comprise a plurality of particles with any of a variety of suitable average particle sizes.
• the plurality of particles has an average characteristic dimension (e.g., an average particle diameter) between greater than or equal to 1 nm and less than or equal to 500 nm.
• the average particle size of the plurality of particles may be determined using SEM, transmission electron microscopy (TEM), and/or atomic force microscopy (AFM).
• the average characteristic dimension of the plurality of particles may be inversely proportional to the discharge current density.
• discharging the electrochemical cell at higher current densities e.g., 500 microamperes/cm 2
• the halogenation layer may have any of a variety of suitable average thicknesses.
• the thickness of the halogenation layer may be measured starting from the active surface of the second electrode, through the bulk of the halogenation layer, to the interface of the halogenation layer and the electrolyte.
• the halogenation layer has an average thickness between greater than or equal to 0.01 micrometers and less than or equal to 5 micrometers).
• the average thickness of the halogenation layer may be determined using XPS depth profiling, SEM, and/or TEM.
• the halogenation layer may substantially cover the surface area of the second electrode. In certain embodiments, for example, the halogenation layer covers between greater than or equal to 10% and less than or equal to 100% of the surface of the surface area of the second electrode.
• the halogenation layer is poly crystalline and/or crystalline.
• the halogenation layer may comprise nanocrystals.
• the crystalline (or polycrystalline) halogenation layer comprises one or more crystallographic defects (e.g., a point defect) and/or grain boundaries, so that the halogenation layer may conduct ions (e.g., from the second electrode, through the halogenation layer, and to an atmosphere surrounding the second electrode, such as an electrolyte).
• crystallographic defects e.g., a point defect
• Methods of determining the crystallinity of the halogenation layer include, for example, TEM (e.g., electron diffraction in TEM) and/or X- ray diffraction (XRD).
• At least a portion of the halogenation layer may be amorphous. It may be advantageous, in certain embodiments, for at least a portion of the halogenation layer to be amorphous because an amorphous halogenation layer may coat a higher surface area of the second electrode as compared to a halogenation layer that is crystalline and/or poly crystalline but otherwise equivalent.
• the electrochemical cell may be a secondary battery (e.g., rechargeable battery).
• the method may further comprise charging the electrochemical cell.
• Charging the electrochemical cell may result in the alkali metal salt (e.g., LiF) in the halogenation layer being electrochemically split, therefore providing an alkali metal ion (Li + ) and a halide ion (e.g., F ).
• the alkali metal ion may be reduced back to an alkali metal at the first electrode (e.g., anode), while the halide ion is incorporated on and/or in the lattice of the second electrode (e.g., cathode).
• the halogenation layer therefore acts as a reservoir of halide ions to be incorporated on and/or in the second electrode of the electrochemical cell as the cell is cycled (e.g., charged and discharged).
• the second electrode comprising the halogenation layer and/or the halide ions may be suitable for use in electrochemical cells, such as a primary battery and/or a secondary battery (e.g., a Li cell and/or a Li-ion cell), to provide lower charging potentials, increased capacities, and increased cyclabilites.
• the electrochemical cell may comprise an electrolyte (e.g., an electrolyte solution).
• the electrolyte is an electrolyte solution comprising, for example, an ionic salt dissolved in a solvent.
• the solvent may be water or an organic solvent, in certain embodiments.
• the electrolyte may comprise dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), dimethylformamide (DMF), dimethylacetamide, a glyme, a carbonate, and/or an ionic liquid. Other solvents are also possible.
• the electrolyte may comprise any of a variety of suitable ionic salts.
• the electrolyte may comprise LiC104, LiPFe, LiBF4, LiCFsSOs, LiNOs, Lil, 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).
• the electrolyte comprises LiC104 dissolved in DMSO. Further details regarding the electrolyte function and composition are described herein.
• the electrolyte comprises the halogenated compound.
• the halogenated compound may be dissolved in any of the aforementioned solvents.
• the halogenated compound may have a relatively high concentration in the electrolyte solvent.
• the halogenated compounds described herein may have a relatively high solubility in the electrolyte solvent.
• 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 more, at 25 °C and 1 atm.
• the solubility of the halogenated compound in the electrolyte is less than or equal to 7 M, less than or equal to 6.5 M, less than or equal to 6.0 M, less than or equal to 5.5 M, less than or equal to 5 M, less than or equal to 4.5 M, less than or equal to 4 M, less than or equal to 3.5 M, less than or equal to 3 M, less than or equal to 2.5 M, less than or equal to 2 M, less than or equal to 1.5 M, less than or equal to 1 M, less than or equal to 500 mM, or less, at 25 °C and 1 atm.
• the solubility of the halogenated compound in the electrolyte is between greater than or equal to 100 mM and less than or equal to 5 M at 25 °C and 1 atm, the solubility of the halogenated compound in the electrolyte is between greater than or equal to 1 M and less than or equal to 2 M at 25 °C and 1 atm).
• the solubility of the halogenated compounds described herein in the electrolyte is greater than the solubility of halogenated gases (e.g., NF 3 and/or SFe), therefore advantageously affording the possibility of electrochemical systems with comparatively higher energy densities.
• the halogenated compound may be employed as an additive, for example, with a relatively low concentration in the electrolyte solvent.
• the solubility of the halogenated compound in the electrolyte when employed as an additive is greater than or equal to 0.1 mM, greater than or equal to 0.5 mM, greater than or equal to 1 mM, greater than or equal to 5 mM, greater than or equal to 10 mM, greater than or equal to 20 mM, greater than or equal to 50 mM, greater than or equal to 100 mM, greater than or equal to 500 mM, or more, at 25 °C and 1 atm.
• the solubility of the halogenated compound in the electrolyte when employed as an additive is less than or equal to IM, less than or equal to 500 mM, less than or equal to 100 mM, less than or equal to 50 mM, less than or equal to 20 mM, less than or equal to 10 mM, less than or equal to 5 mM, less than or equal to 1 mM, less than or equal to 0.5 mM, or less, at 25 °C and 1 atm.
• the solubility of the halogenated compound in the electrolyte when employed as an additive is between greater than or equal to 0.1 mM and less than or equal to 1 M at 25 °C and 1 atm
• the solubility of the halogenated compound in the electrolyte when employed as an additive is between greater than or equal to 1 mM and less than or equal to 5 mM at 25 °C and 1 atm).
• the halogenated compound may be used in neat form, for example, as the electrolyte solvent of the electrochemical cell.
• the electrolyte salt e.g., as explained herein in greater detail
• the halogenated compound may be used in neat form, for example, as the electrolyte solvent of the electrochemical cell.
• the electrolyte salt e.g., as explained herein in greater detail
• the halogenated compound may be used in neat form, for example, as the electrolyte solvent of the electrochemical cell.
• the electrolyte salt e.g., as explained herein in greater detail
• halide ion may, in certain embodiments, be fluoride, chloride, bromide, and/or iodide.
• the halide ion e.g., fluoride
• the fluoride e.g., anhydrous fluoride
• the fluoride may be isolated and used as a reagent in a chemical reaction to generate, for example, one or more fluorinated compounds. Therefore, in certain embodiments, the halogenated compounds described herein may be a source of soluble and/or anhydrous fluoride.
• the electrochemical cell may be a non-rechargeable battery.
• the battery is a primary battery that allows for the safer and/or more complete utilization of the alkali metal and/or the alkaline earth metal, as compared to conventional primary batteries.
• the battery e.g., the primary battery
• the battery may be used in transportation (e.g., electric vehicles, unmanned vehicles), space applications, military applications, implantable/portable medical devices, and/or grid-storage applications (e.g., electrical power grids for the storage of renewable energy).
• the electrochemical cell may be a rechargeable battery.
• the battery is a secondary battery that may cycled (e.g., discharged and charged).
• a system comprising a first electrode comprising an alkali metal and/or an alkaline earth metal, a second electrode, and a halogenated compound comprising a haloalkane associated with a conjugated system via at least one alkene linker or alkyne linker.
• the system is a water remediation system that may be used to reduce halogenated (e.g., fluorinated) compounds present in water, for example, as contaminants.
• the first electrode may comprise a variety of active materials (e.g., anode active materials).
• active materials e.g., anode active materials
• anode active material refers to any electrochemically active species associated with the anode.
• the anode active material is a metal.
• the metal may have a standard reduction potential of less than or equal to about -1.4 V versus the standard hydrogen electrode (SHE).
• the metal and/or the anode may have a standard reduction potential versus SHE of less than or equal to about -1.5 V, less than or equal to about -1.6 V, less than or equal to about -1.8 V, less than or equal to about -2.0 V, less than or equal to about -2.2 V, less than or equal to about -2.4 V, or less than or equal to about -2.5 V.
• the anode active material may comprise lithium, sodium, calcium, magnesium, aluminum, and/or combinations thereof.
• the anode active material may comprise an alkali metal (e.g., lithium, sodium, potassium) and/or an alkaline earth metal (e.g., magnesium, calcium).
• the anode active material may comprise an alkali metal (e.g., lithium, sodium).
• the anode may comprise an alkaline earth metal (e.g., magnesium, calcium).
• 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 foil and lithium deposited on a substrate, lithium alloys (e.g., lithium-aluminum alloys and lithium-tin alloys), and/or three-dimensional materials comprising lithium, such as lithium wicked into a high surface area carbon structure, for example, comprising graphene or graphene oxide. While these materials may be preferred in some embodiments, other cell chemistries are also contemplated.
• the electrodes may comprise one or more binder materials (e.g., polymers, etc.).
• the first electrode may 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 may have a thickness of at least 1 micrometer, at least 5 micrometers, at least 10 micrometers, at least 25 micrometers, at least 50 micrometers, at least 100 micrometers, or at least 150 micrometers. Combinations of the above-referenced ranges are also possible (e.g., from 1 micrometer to 1500 micrometers). Other ranges are also possible.
• the first electrode may comprise 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 reactions between the halogenated compound and the first electrode (e.g., metal in the first electrode).
• the passivation layer may comprise organic compounds, oxides, halides, or combination thereof including but not limited to alkali or metal oxides, carbonates, reduction products of the electrolyte, nitrides, fluorides, chlorides, or a physical protective barrier such as a polymer or conductive ceramic.
• the passivation layer can be formed in a separate chemical step, can be physically placed within the electrochemical cell, or can be formed chemically or electrochemically in situ within the electrochemical cell.
• the second electrode may comprise a variety of active materials (e.g., cathode active materials).
• active materials e.g., cathode active materials
• cathode active material refers to any electrochemically active species associated with the cathode.
• the cathode active material comprises carbon and/or one or more metals.
• the second electrode may have a thickness of less than or equal to 2000 micrometers, less than or equal to 1500 micrometers, less than or equal to 1250 micrometers, less than or equal to 1000 micrometers, less than or equal to 750 micrometers, less than or equal to 500 micrometers, or less than or equal to 200 micrometers.
• the second electrode may have a thickness of at least 1 micrometer, at least 5 micrometers, at least 10 micrometers, at least 25 micrometers, at least 50 micrometers, at least 100 micrometers, or at least 150 micrometers. Combinations of the above-referenced ranges are also possible (e.g., from 1 micrometer to 2000 micrometers). Other ranges are also possible.
• the second electrode may have any suitable surface area. Without being bound by theory, it is believed that efficiency and extent of the electrochemical reaction increases with the surface area of the second electrode (e.g., cathode).
• a second electrode with a relatively high surface area may be used.
• the cathode may have a surface area of greater than or equal to about 10 m 2 /g, greater than or equal to about 250 m 2 /g, greater than or equal to about 500 m 2 /g, greater than or equal to about 750 m 2 /g, greater than or equal to about 1000 m 2 /g, or greater.
• the electrochemical cell comprises an electrolyte.
• the electrolytes used in electrochemical cells can function as a medium for the storage and transport of ions, and in the special case of solid electrolytes and gel electrolytes, these materials may additionally function as a separator between the electrodes. Any liquid, solid, or gel material capable of storing and transporting ions may be used, so long as the material facilitates the transport of ions (e.g., Li ions) between the electrodes.
• the electrolyte is generally electronically non-conductive to prevent short circuiting between the electrodes.
• the electrolyte can comprise 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 may include organic electrolytes comprising one or more materials selected from the group consisting of liquid electrolytes, gel polymer electrolytes, and solid polymer electrolytes.
• an electrochemical cell includes a separator.
• the separator generally comprises a polymeric material (e.g., polymeric material that does or does not swell upon exposure to electrolyte).
• the separator is located between the electrolyte and an electrode (e.g., a first electrode, a second electrode, an anode, a cathode).
• the separator is located between the first electrode (e.g., anode) and the second electrode (e.g., the cathode).
• separator 13 may be located between first electrode 12 (e.g. anode) and second electrode 16 (e.g., cathode).
• the separator may be configured to inhibit (e.g., prevent) physical contact between a first electrode and a second electrode, which could result in short circuiting of the electrochemical cell.
• the separator may be configured to be substantially electronically non-conductive, which can inhibit the degree to which the separator causes short circuiting of the electrochemical cell.
• any of the above groups may be optionally substituted.
• substituted is contemplated to include all permissible substituents of organic compounds, “permissible” being in the context of the chemical rules of valence known to those of ordinary skill in the art.
• substituted whether proceeded by the term “optionally” or not, and substituents contained in formulas of this invention, refer to the replacement of hydrogen radicals in a given structure with the radical of a specified substituent.
• substituent When more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituent may be either the same or different at every position. It will be understood that “substituted” also includes that the substitution results in a stable compound, e.g., which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, etc. In some cases, “substituted” may generally refer to replacement of a hydrogen with a substituent as described herein. However, “substituted,” as used herein, does not encompass replacement and/or alteration of a key functional group by which a molecule is identified, e.g., such that the “substituted” functional group becomes, through substitution, a different functional group.
• a “substituted phenyl group” must still comprise the phenyl moiety and cannot be modified by substitution, in this definition, to become, e.g., a pyridine ring.
• the permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, aromatic and nonaromatic substituents of organic compounds.
• Illustrative substituents include, for example, those described herein.
• the permissible substituents can be one or more and the same or different for appropriate organic compounds.
• the heteroatoms such as nitrogen may have hydrogen substituents and/or any permissible substituents of organic compounds described herein which satisfy the valencies of the heteroatoms.
• 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 this invention are preferably those that result in the formation of stable compounds useful for the formation of an imaging agent or an imaging agent precursor.
• the term “stable,” as used herein, preferably refers to compounds which possess stability sufficient to allow manufacture and which maintain the integrity of the compound for a sufficient period of time to be detected and preferably for a sufficient period of time to be useful for the purposes detailed herein.
• substituents include, but are not limited to, halogen, azide, alkyl, aralkyl, alkenyl, alkynyl, cycloalkyl, hydroxyl, alkoxyl, amino, nitro, sulfhydryl, imino, amido, phosphonate, phosphinate, carbonyl, carboxyl, silyl, ether, alkylthio, sulfonyl, sulfonamido, ketone, aldehyde, ester, heterocyclyl, aromatic or heteroaromatic moieties, -CF3, -CN, aryl, aryloxy, perhaloalkoxy, aralkoxy, heteroaryl, heteroaryloxy, hetero arylalkyl, heteroaralkoxy, azido, amino, halide, alkylthio, oxo, acylalkyl, carboxy esters, carboxamido, acyloxy, aminoalkyl
• the following example describes a family of primary batteries that can deliver large electrical energies through the defluorination of perfluorinated groups, such as perfluoroalkyl groups (RF) and pentafluorosulfanyl (SF5) groups.
• perfluorinated groups such as perfluoroalkyl groups (RF) and pentafluorosulfanyl (SF5) groups.
• a class of perfluorinated group-containing fluoro-aromatics can achieve close-to-full defluorination at practical electrochemical cell operation conditions.
• the structure of the RF- containing aromatics contains three major functional groups: an aromatic group, a perfluroalkane containing group (RF), and optimally an alkene group as the connection between the former two parts.
• RF perfluroalkane containing group
• the SF5 group is directly substituted on the aromatic without an alkene group in between.
• Non-limiting examples of the fluoro-aromatics are shown in FIG. 3.
• the multiple carbon-carbon double bonds facilitate the reductive transformation of the perfluoroalkane groups, defined as C n F2n+i functional groups wherein n is greater than or equal to 2.
• n is greater than or equal to 2.
• a higher fluorine content produces a higher energy density, and as a result, a larger n value can be advantageous.
• too long of a perfluoroalkane chain can cause difficulties in the physical properties of the fluoro-aromatics as well as the ability to achieve a complete discharge of the electrochemical cell.
• the non-limiting examples shown in FIG. 3 are conveniently produced in high yield in one step from commercial starting materials.
• FIG. 4 A typical synthetic procedure to obtain the fluoro-aromatics is shown in FIG. 4.
• a brief description of the synthesis is as follows: A mixture of the aryl bromide (1.0 equivalent), perfluorinated alkene (1.5 equivalents), NaOAc (1.5 equivalents), /i-BmNBr (0.85 equivalents), and palladium catalyst (0.050 equivalents) was dissolved in DMF, and the reaction mixture was stirred for 24-96 hours at 125 °C, or for 1 hour at 200 °C in a microwave reactor. Upon cooling the reaction mixture to RT, the residue was dissolved in AcOEt and HC1. The organic layer was separated, washed with water (x3) and brine, dried with MgSO4, and evaporated to dryness under reduced pressure. The residue was chromatographed on silica gel, and the fraction containing the product was collected and evaporated to dryness.
• Ph-CN-C6 (p) is liquid and miscible with DMSO at RT, but its C8 counterpart is solid at RT and is only soluble at elevated temperatures (e.g., 50 °C).
• the fluoro-aromatics such as Ph-CN-C8 (p), Ph-NO2-C6 (o), and Ph-NO2-C8 (o) exhibit good rate capabilities during discharge.
• FIGs. 7A-7C at 50 °C, all three reactants showed good capacity and voltage retention as the current density increased from 0.04 to 1.0 mA/cm 2 , with capacities of > 1 mAh/cm 2 obtained at such high rate.
• the gravimetric attainable capacities of Ph-CN-C8 (p), Ph-NO2-C6 (o), and Ph-NO2-C8 (o) are 748, 642, and 681 mAh/greactant, respectively.
• the two C8 molecules exhibited slightly higher specific energies (1785 and 1700 Wh/kg re actant for Ph-CN-C8 (p) and PI1-NO2-C8 (o), respectively) than that of the C6 molecule (1600 Wh/kg re actant for Ph- NO2-C6 (o)).
• these numbers are already higher than the theoretical specific energy of SOCI2, which is -1470 Wh/kg re actant, although it is important to note that SOCh-based batteries operate with neat SOCI2 (i.e., without electrolyte diluents).
• RT rate performances for PI1-NO2-C6 (o) and PI1-NO2-C8 (o) are shown in FIGs. 8A-8B. Although both reactants exhibited slightly lower capacities as compared with those obtained at 50 °C (at similar rates), good rate capabilities still persist at RT.
• the achievable specific energy densities at RT for PI1-NO2-C6 (o) and PI1-NO2-C8 (o) are 1470 and 1490 Wh/kg re actant, respectively, which are also comparable with the theoretical energy density of SOCI2.
• LiClCU nonfluorinated salt
• LiF is the only crystallized product that can be detected from X-ray powder diffraction (XRD) after Ph-CN-C8 (p) and Ph-NO2-C6 (o) discharge.
• XRD X-ray powder diffraction
• FIGs. 10A-10C cubic LiF particles were formed on the carbon substrate, the size of which showed significant dependence on the discharge rates.
• the current density increased from 40 to 500 pA/cm 2 , for example, the average LiF particles sizes decreased from -257+47 to - 93+17 nm, i.e., the larger the current density, the smaller the LiF particle sizes. It was concluded that C-F bond breaking is indeed triggered in the cell reduction reactions.
• FIG. 11 shows, for example, the discharge profile of naphthalene molecules functionalized with fluoroalkane.
• the discharge profile in FIG. 11 was evaluated at 50 °C.
• the attainable gravimetrical capacity and average voltage are 840 mAh/greactant and 2.6 V at 50 °C, resulting in a high energy density of 2190 Wh/kgreactant, even higher than that achievable with the Ri -containing aromatics (-1700 Wh/kgreactam).
• the discharge profile at 40 pA/cm 2 and 50 °C was further analyzed (see FIG. 12B), with the low current being closest to equilibrium among the conditions examined. There are two major regions in the discharge curve. The first region has a flat voltage plateau at 2.9 V and contributes > 60% of the total capacity, which corresponds to - 5 e- per molecule.
• the second region has several different voltage steps with a capacity of - 3 c“ pcr molecule, making it 8 e- (calculated based on capacity) transfer in total. It was hypothesized that the first plateau can be attributed to the breaking of the five S-F bonds in the SF5 group, while the second part is a reflective of sulfur reduction, since the multistep profile is very similar to that of S reduction (through polysulfide to Li2S) observed in Li-S batteries.
• LiF particles formed from reduction of PI1-NO2-SF5 was characterized by SEM. See, for example FIGs. 13A-13C.
• FIG. 14 A shows the galvanostatic discharge performances of high concentration PI1-NO2-SF5 cells at 0.3 mA/cm 2 and 50 °C.
• the cells utilized 3 M or 4 M (as indicated) PI1-NO2-SF5 in 0.1 M LiC104/DMS0 as electrolyte, and carbon cathode substrates (12 mm diameter) with a carbon loading of 5 mg/cm 2 .
• FIG. 14B shows the galvanostatic discharge performances of high concentration PI1-NO2-SF5 cells at 0.3 mA/cm 2 and 50 °C.
• the cells utilized 4 M PI1-NO2-SF5 in 0.1 M LiC104/DMS0 as electrolyte, and carbon cathode substrates with a carbon loading of 5 mg/cm 2 .
• a larger cathode substrate (15 mm diameter) was used, thus the unity of the capacity is mAh instead of mAh/cm 2 .
• FIG. 14C shows the galvanostatic discharge performance of high concentration PI1-NO2-SF5 cells at 0.1 mA/cm 2 and RT.
• the cells utilized 4 M PI1-NO2-SF5 in 0.1 M LiC104/DMS0 as electrolyte, and carbon cathode substrates (12 mm diameter) with a carbon loading of 5 mg/cm 2 .
• FIG. 14D shows the galvanostatic discharge performance of high concentration PI1-NO2-SF5 cells at 0.3 mA/cm 2 and 50 °C.
• the cells utilized 200 pL 4 M PI1-NO2-SF5 in 0.2 M LiCWDMSO as electrolyte, and carbon cathode substrates (15 mm diameter) with a carbon loading of 5 mg/cm 2 .
• FIG. 15 shows the attained energy density of PI1-NO2-SF5 cells compared to CF X systems.
• the energy densities were normalized to the weight of the active material, electrolyte, solvent, and carbon.
• the data for CF X was measured using thin CF X electrodes (loading -1 mg/cm 2 ), which were prepared using purchased CF X powders.
• Li-fluoro-aromatic batteries For the disclosed Li-fluoro-aromatic batteries to be comparable with the state-of-the- art Li-CF X batteries, higher reactant concentrations (>2 M) are needed. With a concentration of 0.1 M, DMSO would weigh 20x higher than the reactants, therefore the energy densities normalized to the weight of active materials and electrolyte will be low.
• Li-CF X batteries were compared with the state-of-the-art Li-CF X batteries.
• the discharge performance of Li-CF X cells were measured at 50 °C with purchased CF X powder (coating on Toray paper substrate). Since the laboratory scale cells need excess amount of electrolyte, and the electrolyte weight are typically not reported for commercialized Li-CF X batteries, a CF x -to-electrolyte weight ratio of 1:1 was assumed and the obtained gravimetric energy densities (based on CF X weight) were normalized to the weight of electrolyte+CF x for fair comparisons.
• this electrolyte/CF x weight ratio is a typical value reported in CF X batteries, and thus is a reasonable assumption to represent commercial CF X cells. As is shown in FIG. 16, with a fluoro-aromatic concentration of 2 M or 4 M, it is assumed that the cell will exhibit energy densities comparable to or better than that of the Li-CF X batteries for Ri -containing (-1100 Wh/kg) and SFs-containing (-1500 Wh/kg) aromatics, respectively.
• Li-perfluorinated gas batteries such as Li-SFe and Li-NFs systems
• exhibit high theoretical energy densities 3922 Wh/kg and 5072 Wh/kg for SFe and NF3 respectively
• high chemical stabilities and thus are promising electrochemically- active components for primary battery applications.
• the gaseous molecules however, have low solubility in the non-aqueous electrolytes and an electrode adsorption process is required before the molecules can be successfully reduced, which is challenging with symmetric perfluorinated (i.e., inert) reactants. Therefore, large overpotentials were observed during discharge.
• a second practical consideration is that the gaseous systems also require a gaseous headspace in the electrochemical cell set up, which may further burden the cell-level energy densities.
• Li-perfluoroalkyl iodide batteries were developed that utilize fluorinated liquids as cathodes.
• the commercially available reactants which have an RF chain directly connect to an iodine (I) in each molecule, are widely used as building blocks in organic synthesis.
• the reactants were used as model systems to demonstrate that the RT reduction of the RF chain is achievable at high potentials (up to 3.0 V) and in a single cell setup.
• the close-to-full defluorination of the reactants was not achieved. Therefore, further optimizations are still needed for the Li-perfluoroalkyl iodide batteries to be feasible for practical applications.
• the molecular structures of the aforementioned commercialized cathodes are relatively simple and hard to modify, thus to improve the cell performances, one needs to focus on other cell components, such as electrolytes, supporting carbon, or catalysts.
• fluoro-aromatic molecules allow multiple types of modification (ring structure, substituent type and position, RF chain length, fluorinated group species, etc.), which can directly affect the reduction nature of these molecules. This not only provides more opportunities for electrochemical performance improvement, but also serves as a new platform to investigate fluoride bond reduction, thus bring more scientific insights to chemical and electrochemical research.
• the role of the 7t-electrons and substituents in the fluoro-aromatics is critical to achieve the full reduction and hence the optimal energy density.
• This enhancement may be the result of increased charge transport and potentially creating transient or persistent carbon containing products that facilitate charge transport.
• Optimizing interfacial interactions between the flouro-aromatics and the anode is also key, and fluorine materials can display what is known as the fluorous-effect, wherein they become immiscible with other organic materials and may not optimally wet the interface with the electrode.
• these interfaces can be modified with groups containing perfluoroalkanes or perfluoro-aromatics. It is also shown that different substituents attached to the aromatic rings can give different discharge characteristics.
• a mixture of different reducible fluoro-aromatics will provide for the desired performance. Considerations include long-term stability, power output, and energy density.
• the disclosed fluoro-aromatic battery systems have the potential to deliver high celllevel energy densities with high rate capabilities, comparable to or even better than that of the state-of-the-art Li-CF X batteries.
• the technology is of high value for implantable devices (e.g., cardiac pacemakers), on-ship power, remote human operation (e.g., space exploration), memory or emergency backups, military applications, and other electronic devices.
• Two-electrode Swagelok-type Li cells were constructed in an argon glovebox, with the dried KB cathode and a 9 mm diameter disk of Li metal as anode (0.75 mm thick, 99.9% metals basis, Alfa Aesar), which was pre-stabilized by soaking in pure CeF 131 (99%, Sigma- Aldrich) for at least three days prior to use.
• the separator 13 mm diameter glass fiber filter paper
• 50 pL electrolyte solution (as indicated in text).
• the cells were rested at open circuit voltage (OCV) for 5 h before the galvanostatic discharge tests, which were carried out (BioLogic VMP3 potentiostat or MPG2 workstation) at the specified current density with a voltage window ranging from OCV to a lower cutoff voltage of 1.9 V vs Li/Li + .
• OCV open circuit voltage
• MPG2 workstation BioLogic VMP3 potentiostat or MPG2 workstation
• the following example describes high energy Li primary battery cathodes that utilize the defluorination of perfluorinated groups, such as pentafluorosulfanyl (SFs) groups.
• perfluorinated groups such as pentafluorosulfanyl (SFs) groups.
• FIG. 18 Intrinsic electro activity of R-Ph-SFs molecules: It is demonstrated that the design strategy of SFs-containing compounds is applicable to various R-group functionalities and positions, and the number of perfluorinated SFs groups is not restricted to one. Suitable reactant structures comprising a sulfur-pentafluoride group, for example, are shown in FIG. 18. To examine the intrinsic redox behavior, FIGs. 19A and 19B show discharge of cells containing 0.1 M R-Ph-SFs at 40 p A/cm 2 , with capacities normalized to reactant weight (FIG. 19A) and electrons reacted per molecule (FIG. 19B).
• the cells were discharged with 0.1 M R-Ph-SFs / 0.1 M LiC DMSO as catholyte and Ketjen Black as cathode substrate at 40 pA-cm’ 2 .
• the cells were tested at 50 °C to maximize capacity.
• Unsubstituted Ph-SFs and Ph-I-SFs exhibited modest voltages of ⁇ 2.5 V vs. Li/Li + over a single plateau.
• the discharge of a reactant containing two -SF5 groups was next examined at RT, and the results are shown in FIGs. 20A-20B.
• the cell was discharged with 0.1 M Br-Ph-2SFs / 0.1 M LiCK DMSO as catholyte and carbon foam as cathode substrate at 40 pA-cm’ 2 and RT.
• the Li-Br-Ph-2SFs cell exhibits two discharge plateaus at 2.6 and 2.2 V vs. Li/Li + , each corresponds to a capacity ⁇ 6 e“/molecule, which might be attributed to the reduction of the two -SF5 groups.
• a low voltage ( ⁇ 2.0 V vs. Li/Li + ) tail was observed at the end of discharge, suggesting the continue reduction of the aromatic components. Overall, a total capacity of 1138 mAh/gBr-ph-2SF5 was obtained.
• O content in the cathode also increased from 16.8 to 27.0 at.% between 2.07 and 1.90 V vs. Li/Li + (FIG. 21D), while corresponding SEM images indicated nucleation of a new phase with spherical morphology (FIG. 21B), confirmed to be O-rich and N, F, S-poor by energy-dispersive X-ray (EDX) analysis.
• EDX energy-dispersive X-ray
• FIG. 22C The solid line in FIG. 22C is the projected pressure baseline, which is extrapolated from the linear fit of cell pressure profile during post-discharge resting (for 10 hours).
• the cell in FIG. 22C was discharged with 150 pL 0.1 M NO2-PI1-SF5 / 0.1 M LiC104 / DMSO electrolyte and KB electrode at 40 pA-cm’ 2 and 50 °C.
• FIG. 23A shows galvanostatic discharge at concentrations of 1-5 M at 40 pA/cm 2 and 50 C C, where capacities are normalized to the weight of NO2-PI1-SF5 as an intrinsic measure of reactant utilization.
• Discharge at concentrations of 1.0-2.0 M led to attainable capacities of 818 and 786 mAh-gNO2-Ph-SF5 1 respectively, with retention of a similar discharge profile. Further increasing concentration (>3 M) saw disappearance of the lower- voltage plateau at ⁇ 2.1 V vs.
• FIG. 23A shows these sub-stack capacities and gravimetric energies at a slightly higher current of 0.1 mA-cnT 2 .
• Theoretical capacities correspond to 8 e- per molecule. Capacities increased from 292 to 362 mAh-gsub-stack’ 1 as concentration increased from 3 M to 4 M, beyond which further gains were negligible. The maximum gravimetric energy of 1085 Wh-kgsub-stack’ 1 was obtained at 4.5 M. Capacity and energy decreased with concentrations exceeding 4.5 M due to diminishing supporting solvent (DMSO, -16 wt.% of the catholyte at 5 M), which led to significant decline in ionic conductivity from 6.4 to 0.6 mS'cm' 1 from 0.1 M to 5 M (FIG. 24). Additionally, low DMSO content decreases the ability to solubilize LiF, making electrode passivation effects more severe.
• DMSO supporting solvent
• FIG. 23D The rate capability of cells at 4.0 M concentration and 50 °C is shown in FIG. 23D.
• Capacities remained constant at -362 mAh-gsub-stack 1 from 0.3 - 1.0 mA-crn’ 2 (0.01 C - 0.04 C) and decreased moderately thereafter up to 3 mA-cnT 2 (0.12 C), indicating excellent rate capability.
• FIG. 25 shows that as-assembled Li-NO2-Ph-SFs cells rested for 30 days at 50 °C exhibited no capacity loss upon subsequent discharge, and cells also exhibited negligible voltage fade upon interruption at partial depth- of-discharge and resting for 10-30 days, indicating good shelf life characteristics.
• Li-CF X cells were assembled and tested. The breakdown of the cell masses is shown in FIG. 26A.
• Typical electrolyte-to-active solid mass fractions in commercial cells range from 0.7-1.3, a lean electrolyte loading that is challenging to achieve in-house. Consequently, Li-CF X cells (20.4 ⁇ 2.3 mg of CF x , 11.5 ⁇ 1.3 mg-cm' 2 loading) were tested in a flooded electrolyte configuration but normalized assuming a 1:1 electrolyte:cathode mass ratio dictated by commercial standards.
• Li-NO2-Ph-SFs cells the active material is in the liquid phase, hence design considerations favor a substantially larger electrolyte-to-solid ratio (carbon being electrochemically inactive) of -8:1 w/w, with 5 mg-cm’ 2 of carbon and -28 mg-cm’ 2 of NO2-PI1-SF5 for 4 M concentration.
• a Ragone plot (FIG. 26B) shows that Li-NO2-Ph-SFs cells attain comparable sub-stack level performance to Li-CF X cells at low power (-1000 Wh-kgsub-stack’ 1 at -15 W-kgsub-stack’ 1 ).
• the average value and error bars are based on three cells each.
• Li-NO2-Ph-SFs cells show advantages over Li-CF X at moderate powers (50-100 W-kgsub-stack’ 1 ), which is attributed to facile kinetics in the liquid phase. These gains diminish at higher powers (>150 W-kgsub-stack’ 1 ) for this particular formulation due to limitations of ionic conductivity of NCh-Ph-SFs-based electrolytes.
• Hybrid solid-liquid cell design The chemical compatibility and voltage matching of Li-NCh-Ph-SFs and Li-CF X creates new possibilities to design hybrid cell concepts that surpass the gravimetric energy of any known formulation. To demonstrate this, cells containing a NCh-Ph-SFsiCFx mass ratio of ⁇ 2:1 were designed (FIG. 26A). The total substack percentage of active materials was -80%, compared to the Li-CF X (-50%) or Li-NCh- Ph-SFs cells (-70%).
• a gravimetric capacity of 421 mAh-gsub-stack’ 1 was obtained at 0.1 mA'cm' 2 and 50 °C with the hybrid cell, significantly higher than the respective individual cells ( ⁇ 362 mAh-gsub-stack’ 1 , FIG. 26C).
• ‘Sub-stack’ for Li-CF X denotes CF X + electrolyte + carbon + consumed Li; for hybrid cells, the weight of NO2-PI1-SF5 is also included.
• the gravimetric energy, reaching 1195 Wh-kgsub-stack’ 1 at 5 W-kgsub-stack’ 1 represents a -20% improvement over Li-CF X at the sub-stack level (FIG. 26B). SEM images (FIG.
• Li-NO2-Ph-SFs cells The potential of Li-NO2-Ph-SFs cells was next examined as a secondary (i.e., rechargeable) battery.
• Cells with 0.1 M NO2-PI1-SF5 were first discharged at a high rate of 0.3 mA/cm 2 , to promote the formation of small particle sized LiF, and subsequently charged at 0.04 mA/cm 2 .
• DMSO ethylene carbonate/dimethyl carbonate
• EC/DMC ethylene carbonate/dimethyl carbonate
• FIG. 28 The profiles of the initial discharge and the following two cycles at 50 °C are shown in FIG. 28.
• cells with EC/DMC were cycled between 1.5-4.6 V vs. Li/Li + , while that with DMSO was cycled between 1.9-3.9 V vs. Li/Li + .
• cells with DMSO exhibited multiple voltage plateaus similar to that observed during first discharge (after the high voltage plateau), corresponding to a capacity of 0.26 mAh/cm 2 or 2.2 e“/molecule.
• a similar discharge profile was retained during the third discharge, with capacity faded to ⁇ 1.3 e“/molecule.
• the total capacity of the two discharges (821 mAh/gph-NO2-SF5) was compared to the theoretical capacity of the high voltage plateau (538-646 mAh/gNO2-Ph-SF5, assuming 5-6 electron transfer).
• the total discharge capacity of the first two discharges exceeds the theoretical value, suggesting that -200 mAh/gph-NO2-SF5 capacity is reversible, which is further confirmed by the > 200 mAh/g/gph-NO2-SF5 capacity observed during the third discharge, where the effect of unreacted NO2-PI1-SF5 can be eliminated.
• a weaker binding metal such as Na
• FIG. 31 The discharge of NO2-PI1-SF5 catholyte with divalent metal anode, Ca, is shown in FIG. 31.
• Cells utilized 4 M NO2-PI1-SF5 / 0.2 M CaTFSI / DMSO as catholyte, and were discharged at 0.04 mA/cm 2 at 50 °C. A total capacity of 6.5 mAh/cm 2 was obtained, initiating at a voltage of 0.8 V vs. Ca/Ca 2+ .
• the large overpotential (-2 V lower cell voltage than that observed in Li system) might partially be attributed to the passivating solid electrolyte interphase (SEI) generated at the surface of Ca anode.
• SEI solid electrolyte interphase
• a reference to “A and/or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.
• the phrase “at least one,” in reference 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 within the list of elements and not excluding any combinations of elements in the list of elements.
• This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified.
• “at least one of A and B” can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.

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