Electrolyte systems including components for improving the performance of lithium-based secondary batteries

Abstract

The numerous problems of prior art lithium-based batteries, particularly its electrolyte system, including but not limited to polysulfide shuttling, formation of lithium dendrites and dead lithium during stripping and plating, thermal runaway, volume expansion, and stringent requirements on electrolyte composition, are well documented in the prior art and remain the main obstacles to realizing the exceptional potential of lithium-based batteries as the ideal energy storage solution. The inventive concept presented herein addresses the challenges with a multi-pronged approach that radically changes the electrolyte system in different ways to produce synergistic benefits within each approach and particularly in a combined manner. The inventive concept improves the electrolyte system in terms of solvents, electron-withdrawing compounds, lithium-ion transport compounds, performance-enhancing additives, and chalcogenides. These advances provide benefits including improved charge / discharge capacity, coulombic efficiency, cycle life, sulfur optimization, oxidation stability, etc., while reducing polysulfide shuttling and lithium dendrite formation, among other benefits.

Description

[0001] Related applications This application relates to and claims priority to U.S. Provisional Patent Application No. 63 / 562,167, filed March 6, 2024, entitled “ELECTROLYTE ADDITIVE FOR IMPROVING PERFORMANCE AND CYCLE LIFE OF LITHIUM-BASED SECONDARY BATTERIES”, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0002] This invention relates to battery technology, and more specifically to novel electrolyte compositions comprising various components such as solvents, electron-withdrawing compounds, and / or additives, which, individually or in any combination, reduce manufacturing costs and complexity, and result in lithium-based electrochemical single-cell batteries with lower mass, higher energy density, and longer cycle life. Exemplary components include, but are not limited to, chalcogenides, α-hydrogenated selectively β-functionalized compounds, and / or additives. Background Technology

[0003] Batteries, especially lithium-based batteries, remain a focus of attention due to their high theoretical energy density, light weight, low cost, and other well-proven advantages in the field. However, issues such as polysulfide shuttle, formation of lithium dendrites and dead lithium during stripping and plating, thermal runaway, volume expansion, and stringent requirements for electrolyte composition remain challenges to the large-scale adoption of lithium-based batteries in a variety of applications.

[0004] For reasons well known to those skilled in the art, solvents in lithium-based (especially lithium-sulfur-based) batteries have more stringent requirements than those in other battery chemistry systems, including but not limited to the following: (1) reducing stability relative to lithium metal and lithium alloys, which limits suitable solvents to those with high least unoccupied molecular orbitals (LUMOs) and low donor numbers, typically around 1.8V or lower; (2) strong oxidative stability to the cathode material (typically sulfur-based or carbon-based), which excludes compounds with high (around 2.45V or higher) highest occupied molecular orbitals (HOMOs), and is typically achieved through highly fluorinated solvent components; (3) a strong ability to form a solvent / electrolyte interface (SEI), for example by forming LiF, Li3N, and / or Li2O on the surface of the anode; (4) electrolysis The balance between the overall solubilizing ability of the electrolyte to lithium polysulfides and the solubilizing ability of the electrolyte to the specific types of lithium polysulfides formed in the electrolyte is finely tuned. This is typically achieved by promoting the formation of long-chain (e.g., Li2S8) rather than short-chain (e.g., Li2S2, Li2S4, Li2S3, etc.) lithium polysulfides to facilitate the pathway to elemental sulfur; (5) high solubilizing ability of lithium salts (especially lithium nitrate, which is an important additive for combining reduced lithium metal with oxidizing polysulfides); (6) low density to minimize the percentage of battery weight conferred by the electrolyte; (7) high boiling point (for safety and ease of manufacture, as briefly discussed above); and (8) avoidance of electrophilic agents (e.g., carbonates commonly used in Li-ion batteries) to avoid strong nucleophilic reactions with polysulfides.

[0005] Due to these stringent requirements, typical solvent systems used in lithium-based batteries include at least two solvents (one acting as a solvator and the other as a diluent) and possibly additional components such as lithium salts and redox mediators, which in turn increases the solvent's contribution to the battery's total weight. This exacerbates manufacturing concerns and impairs the overall efficiency of the battery in use. Furthermore, the low boiling points of the solvents commonly used in lithium-based batteries raise safety concerns due to their flammability or explosiveness, potentially caused by short circuits that may form within the battery during use.

[0006] Furthermore, as is well known in the art, lithium-based (particularly lithium-sulfur-based) battery chemistry involves parasitic reactions between the lithium active material and sulfur at the anode due to the formation of lithium polysulfides. These reactions effectively reduce the amount of active electrode material used in electrochemical single-cell batteries to perform electrical functions and adversely affect the overall performance (particularly energy efficiency) of batteries based on such lithium chemistry systems. In particular, the practical limitations observed in lithium-based (particularly lithium-sulfur-based) batteries are attributed to the kinetic limitations of the reduction-oxidation (redox) reaction that converts (poly)sulfides from the liquid phase to the solid phase and ultimately back to elemental lithium. The main mechanisms for the conversion of lithium polysulfides to elemental lithium are given in Equations 0 and 1(a)-(d) below. Furthermore, as is known in the art, the kinetics of solid-solid phase reactions tend to be slower than those of liquid-solid phase reactions, which in turn tend to be slower than liquid-liquid phase interactions. Therefore, the rate-limiting processes for the conversion of lithium polysulfides tend to be those shown in Equations 1(c) and 1(d). Therefore, mitigating the negative impact of such parasitic reactions on the conversion of lithium polysulfides into pure lithium is a significant obstacle to achieving the ideal performance of lithium-based battery technology.

[0007] Conventional methods for improving the specific energy and / or energy density of lithium-based batteries (especially lithium-sulfur batteries) focus on optimizing the structure and composition of sulfur-based cathodes, adjusting the amount of electrolyte used in electrochemical cells, using well-structured carbon frameworks to improve volumetric energy density, optimizing pore framework geometry to increase sulfur loading within electrochemical cells, and including additives in the electrolyte to mitigate polysulfide dissolution within electrochemical cells during cycling.

[0008] Focusing on electrolyte composition, Zhao et al. recently investigated the use of chalcogenides (compounds known in the art, including chalcogenide components such as sulfur, selenium, tellurium, etc., and electropositive components) as redox co-mediators to promote sulfur redox kinetics in lithium-sulfur batteries. Their work is described in "An Organoselenide Comediator to Facilitate SulfurRedox Kinetics in Lithium-Sulfur Batteries". Adv. Mater.In 2007798 (2021), Zhao reported the use of diphenyldiselenoether (DPDSe) in a conventional electrolyte system. This conventional electrolyte system consisted of 1:1 (v:v) 1,2-dimethoxyethane (DME) and 1,3-dioxolane (DOL) as solvents, 1M lithium bis(trifluoromethane)sulfonylimide (LiTFSI) and 2.0 wt% lithium nitrate (LiNO3) as lithium-ion sources, and 100 mM DPDSe as a redox co-mediator. The resulting Li-S electrochemical single-cell battery exhibited a rate performance of 817 mAh / g at 2 C and a practical initial energy density of 301 Wh / kg, but only stabilized for 30 cycles. The stability loss was defined as the point (cycle number) at which the single-cell battery exhibited 60% or less of its initial capacity.

[0009] In “Promoting the sulfur redox kinetics by mixed organodiselenides inhigh-energy-density lithium-sulfur batteries” eScience In 1:44-52 (2021), Zhao reported a similar electrolyte system, but with a mixture of dimethyl diselenyl ether (DMDSe) and DPDSe as a redox co-mediator. The resulting Li-S pouch cell exhibited a capacity retention of 81.6% after 200 cycles at 0.5 C and a high initial capacity of 1002 mAh g⁻¹ at 0.1 C, with a sulfur loading of approximately 1.2 mg / cm³. 2 At higher loading rates, such as approximately 4.9 mg / cm³ 2 Up to approximately 6.1 mg / cm 2 Stability was maintained for up to 50 cycles (Zhao did not report stability exceeding this number of cycles for implementations with higher loads).

[0010] Building on Zhao's work, Liu et al. published "An Organodiselenide Comediator to Facilitate Sulfur Redox Kinetics in Lithium-Sulfur Batteries with Encapsulating Lithium Polysulfide Electrolyte". Angewandte Chemi Inter. An electrolyte system was developed in 62:30 (2023) which includes 20m as a redox co-mediator. MA solvent mixture of DMDSe and DME / DOL / 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) in a volume ratio (v / v / v) of 2:2:1, and 1... M The cell contains LiTFSi and 2 wt% LiNO3. The single-cell battery is characterized by a sulfur loading of 4.0 g / cm³. 2 The DME / DOL / TTE solvent system forms an encapsulated lithium polysulfide electrolyte (EPSE) structure, which mitigates parasitic reactions between lithium polysulfides and the lithium metal anode. However, as is known in the art, the cathode sulfur redox kinetics are inevitably sacrificed due to the barrier effect of the outer solvated shell formed by hydrofluoroethers and other shell solvents. Furthermore, Liu's single-cell battery suffered a loss of approximately 65 mAh / g in initial cycle discharge capacity and maintained this for 40 cycles (at which point testing was stopped due to the failure of the control cell). Liu's single-cell battery could only be charged at a maximum of 0.2 C, and its average discharge capacity above this rate was less than half that of the control. Therefore, Liu's electrolyte sacrificed discharge capacity and rate performance, although cycle stability was improved. Overall, Liu reported similar results to Zhao's initial report of a Li–S pouch cell with an actual energy density of 359 Wh / kg and a stable lifetime of only 37 cycles.

[0011] Therefore, existing attempts to improve sulfur utilization in lithium-based electrochemical single-cell batteries by including chalcogenides in the electrolyte formulation suffer from short cycle life (e.g., about 20-50 cycles or less, especially at 4.0 g / cm³). 2 Problems with low charge rates (e.g., about 0.5 C, typically below 0.3 C, and as low as 0.025 C), discharge rates, and rate performance (especially when the solvent component of the electrolyte system includes hydrofluoroethers or other similar electron-withdrawing compounds as described herein or as would be thought by one of ordinary skill in the art upon reading this disclosure).

[0012] Therefore, there has long been a need to improve electrolyte composition to address the aforementioned and / or other problems associated with existing technologies. Summary of the Invention

[0013] Based on the various aspects, embodiments, and implementation schemes of the inventive concept presented herein, material compositions, suitable systems for implementing said material compositions, methods for preparing such material compositions and corresponding systems, and various applications for improving properties such as coulombic efficiency and cycle life of lithium-based (especially lithium-sulfur) secondary batteries are disclosed.

[0014] Generally, according to the selected embodiments, the present invention concept includes an electrolyte system and techniques for preparing and using the electrolyte system, which includes: (1) a solvent system, (2) at least one electron-withdrawing compound, (3) one or more lithium-ion transport compounds, (4) at least one chalcogenide, and / or (5) one or more performance-enhancing additives configured to improve the coulombic efficiency and cycle life of a battery in which said electrolyte system is implemented. Furthermore, said electrolyte system generally meets the stringent requirements described above to optimize operating characteristics while minimizing weight and environmental impact during manufacturing and use.

[0015] The solvent system may include a variety of components that play different but related roles, such as solvation ability, dilution (for improving wettability), or to promote certain chemical reactions within the electrolyte system, particularly the conversion of polysulfides to lower redox states and / or the redox reaction of elemental lithium.

[0016] These components can be selected from the exemplary substances described herein and can be present in any amount suitable for enabling an electrochemical single-cell battery to operate, for example, up to about 100% by volume of the electrolyte system composition, wherein other components such as lithium-ion transport compounds and / or performance-enhancing additives are partially or completely solvated therein. Preferably, the components are present in an amount suitable for enabling an electrochemical single-cell battery to operate, the electrochemical single-cell battery having an anode comprising lithium or lithium-based materials as active materials.

[0017] In various methods, solvents and electron-withdrawing compounds may be present cumulatively in amounts ranging from non-zero up to about 75 vol%. "Costally present" means that multiple substances of a given type of component are present in the aforementioned cumulative amounts. For example, for a solvent with a cumulative amount of 25 vol%, three different solvent substances may be present in amounts of about 5 vol%, about 5 vol%, and about 15 vol%, respectively.

[0018] According to various implementation schemes, lithium-ion transport compounds can be used at approximately 0.1 M To about 10 M A quantity of any value within or between a range exists cumulatively.

[0019] In different implementations, the performance-enhancing additive can be in the range up to about 0.2. M The non-zero quantities exist cumulatively.

[0020] Depending on the chosen method, the solvent system may include a single solvent or a combination of solvents, which may be independently characterized by different solvation capabilities. For example, an exemplary solvent system may include a first solvent with high solvation capability for salts (such as lithium-ion transport compounds described herein), while a second solvent may have low solvation activity for lithium-ion transport compounds but high solvation activity for other compounds (such as polar, nonpolar, aqueous, organic, etc. compounds).

[0021] Furthermore, the combination of solvents may include a variety of solvents having similar solvation capabilities and / or activities, particularly where such solvents can cooperatively or synergistically solvate a suitable solute, as will be understood by those skilled in the art upon reading this disclosure.

[0022] Furthermore, the specific solvents included in a given solvent system may be selected based on the specific application of the intended electrochemical cell, the composition of other components of the electrolyte system, the composition of other components of the electrochemical cell (such as the anode, cathode, and / or separator), or other factors that a person skilled in the art will understand after reading this disclosure.

[0023] According to various embodiments, suitable solvents may be selected from examples such as: dimethoxyethane (DME), dioxolane (DOL), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), toluene, tetramethylurea (TMU), tetrabutylammonium hydroxide (TBA), dimethylacetamide (DMA), tetrahydrofuran (THF), diethylene glycol dimethyl ether (diethylene glycol dimethyl ether or DEGDME), acetonitrile (ACN), dimethyl trisulfide (DMTS), diisopropyl ether (DIPE), tetrahydrofuran (THF), 1,2 -Diaminopropane (DAP), Triethylene glycol dimethyl ether (trigDME), Tetraethylene glycol dimethyl ether (TEGDME), Sulfolane (SUL), Methyl tert-butyl ether (MTBE), 2,2,3,3-Tetrafluoro-1,4-dimethoxybutane (FDMB), Bis(2,2,2,trifluoroethyl) ether (BTFE), 1H,1H,5H-Otafluoropentyl 1,1,2,2-tetrafluoroethyl ether (OFE), (1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl) Ethers (TTE), 2,2,2-trifluoroethyl 1,1,2,2-tetrafluoroethyl ether (TFETFE), 1,1,2,2-tetrafluoroethyl isobutyl ether (TFEIE), 1,1,2,3,3,3-hexafluoropropyl 2,2,2-trifluoroethyl ether (THE), perfluoromethoxybutane (MPB), bis(2,2-difluoroethyl) ether (DFE), 2,2,2-trifluoroethyl methyl ether (TFEME), bis(2-fluoroethyl) ether (BFE), bis(2,2,2,trifluoroethyl) ether (BTFE), 3-fluoro Pyridine (3FP), 1,2-(1,1,2,2-tetrafluoroethoxy)ethane (TFEE), 1,2-dimethoxy-1,1,2,2-tetrafluoroethane (DMETF), 2-methyl-1-(1,1,2,2-tetrafluoroethoxy)propane (TFEIBE), bis(2,2,3,3,3-pentafluoropropyl) ether (BPFPE), allyl 2,2,3,3,3-pentafluoropropyl ether (APFPE), hydrocarbons such as toluene, benzene, hexane, or any combination or equivalent thereof that would come to mind by a person skilled in the art upon reading this disclosure.

[0024] According to various exemplary embodiments, the solvent may be present cumulatively in amounts of about 1 volume%, about 2.5 volume%, about 3.33 volume%, about 5 volume%, about 6.66 volume%, about 7.5 volume%, about 10 volume%, about 12.5 volume%, about 15 volume%, about 17.5 volume%, about 20 volume%, about 25 volume%, about 30 volume%, about 33 volume%, about 35 volume%, about 40 volume%, about 50 volume%, about 60 volume%, about 66.6 volume%, about 70 volume%, or about 75 volume%.

[0025] Depending on the implementation, the electrolyte system may include a single electron-withdrawing compound or a combination thereof. Similar to solvent systems, the specific electron-withdrawing compounds included in a given electrolyte system may be selected based on the specific application of the electrochemical cell for which performance-enhancing additives are to be utilized, the chemical activity of the electron-withdrawing compounds (particularly how the electron-withdrawing compounds may decompose during operation of the resulting electrochemical cell to which they are to be implemented, and how such derivatives or the electron-withdrawing compounds themselves may interact with the electrodes and form a solid-electrolyte interface (SEI) therewith), the composition of other components of the electrolyte system, the composition of other components of the electrochemical cell (such as the anode, cathode, and / or separator), or other factors that a person skilled in the art will understand upon reading this disclosure.

[0026] Electron-withdrawing compounds preferably contain at least one α-hydrogenated selective β-functionalized unit, and more preferably, the at least one α-hydrogenated selective β-functionalized unit does not contain fluorine. For example, in various embodiments, electron-withdrawing compounds may include 2,2-dimethoxy-4-trifluoromethyl-1,3-dioxolane (DTDL), 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG), 1,1,1,14,14,14-hexafluoro-3,6,9,12-tetraoxatetradecane (FTrG), 1,1,1,17,17,17-hexafluoro-3,6,9,12,15-pentaheptadecane (FTeG), bis(2,2-difluoroethyl) ether (BDE), bis(2,2,2,trifluoroethyl) ether (BTFE), 2,2,2-trifluoroethyl 2-fluoroethyl ether (TFFE), 1, 1-Difluoroethyl-2-fluoroethyl ether (DFE), fluorinated 1,4-dimethoxybutane (FDMB), 3-fluoropyridine (3FP), 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,3,3-tetrafluoropropyl) ether (BTFPE), 2,2,2-trifluoroethyl 1,1,2,2-tetrafluoroethyl ether (TFTFE), tris(2,2,2-trifluoroethyl) phosphate, bis(2,2,2-trifluoroethyl) methylphosphonate, isosorbide dinitrate (ISDN), bis(2-fluoroethyl) ether (BFE), or other suitable equivalents that a person skilled in the art will understand after reading this specification, and any arrangement or combination of the foregoing substances.

[0027] Furthermore, the derivatives of the electron-withdrawing compound preferably contain lithium-ionized fluoroalkoxides, such as trifluoroethanol and / or lithium trifluoroacetate.

[0028] According to various implementation schemes, electron-withdrawing compounds may be present cumulatively in amounts of about 1 vol%, about 2.5 vol%, about 3.33 vol%, about 5 vol%, about 6.66 vol%, about 7.5 vol%, about 10 vol%, about 12.5 vol%, about 15 vol%, about 17.5 vol%, about 20 vol%, about 25 vol%, about 30 vol%, about 33 vol%, about 35 vol%, about 40 vol%, about 50 vol%, about 60 vol%, about 66.6 vol%, about 70 vol%, or about 75 vol%.

[0029] Depending on the chosen method, the solvent and electron-withdrawing compound may be present relative to each other in a specific volume ratio. Exemplary ratios may include approximately 1:1, approximately 1:2, approximately 1:3, approximately 1:5, approximately 1:10, approximately 2:1, approximately 3:1, approximately 5:1, approximately 10:1, approximately 2:3, approximately 3:4, approximately 2:5, etc. (volume% solvent:volume% electron-withdrawing compound). In embodiments where multiple solvents and / or electron-withdrawing compounds are present, these components may also be present relative to each other in a specific volume ratio, as exemplified above regarding the solvent:electron-withdrawing compound ratio.

[0030] Of course, it will be understood that, in the context of the inventive concept described herein, the relative amounts of solvent and electron-withdrawing compound can be any values ​​within the wide range given above. Different amounts of solvent and electron-withdrawing compound can be selected based on the specific application of the electrochemical cell utilizing the electrolyte system and / or the composition of other components, based on the composition of other components of the electrochemical cell (such as the anode, cathode, and / or separator), and / or based on the composition and / or amount of other components of the electrolyte system (such as the composition and / or amount of performance-enhancing additives, lithium-ion transport compounds, etc.), as will be understood by those skilled in the art upon reading this disclosure.

[0031] Based on the selected illustrative implementation scheme, various embodiments with suitable solvent system compositions are given in Table 2 below with the aid of examples.

[0032] In addition, depending on the implementation method, the electrolyte system may (and preferably does) include additional components, such as lithium-ion transport compounds and / or performance-enhancing additives.

[0033] In various methods, the lithium-ion transport compound may include any one or more compounds known in the art to promote lithium-ion transport under conditions present in lithium-based batteries as disclosed herein. More preferably, the lithium-ion transport compound does not conduct polysulfides.

[0034] As noted above regarding solvents and electron-withdrawing compounds, a particular lithium-ion transport compound included in a given electrolyte system may be selected based on the degree of lithium-ion transport capability, the specific type of lithium ions that the compound can transport, the specific application of the intended electrochemical cell, the composition of other components of the electrolyte system, the composition of other components of the electrochemical cell (such as the anode, cathode, and / or separator), or other factors that a person skilled in the art will understand after reading this disclosure.

[0035] For example, suitable lithium-ion transport compounds may include lithium, and may be salts of lithium. Exemplary types of lithium-ion transport compounds suitable for use in the context of the presently disclosed inventive concept include, but are not limited to, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO3), lithium perchlorate (LiClO4), lithium difluoro(oxaloyl)borate (LiDFOB), lithium bis(oxaloyl)borate (LiBOB), lithium trifluoromethanesulfonate (LiTf), lithium bis(pentafluoroethanesulfonyl)imide (LiBETi), lithium bis(fluorosulfonyl)imide (LiFSI), lithium trifluoroacetate (LiTFAc), or any suitable combination and / or equivalent thereof that would arise to a person skilled in the art upon reading this disclosure.

[0036] Preferably, according to various methods, the lithium-ion transport compound is present in an amount ranging from about 0.1 M to about 10 M or in any value between therebetween, such as about 0.2 M, about 0.25 M, about 0.33 M, about 0.4 M, about 0.5 M, about 0.66 M, about 0.75 M, about 0.85 M, about 0.9 M, about 0.95 M, about 0.99 M, about 1.0 M, about 1.25 M, about 1.33 M, about 1.5 M, about 1.66 M, about 1.75 M, about 2.0 M, about 2.25 M, about 2.33 M, about 2.5 M, about 2.66 M, about 2.75 M, about 3.0 M, about 3.25 M, about 3.33 M, about 3.5 M, about 3.66 M, about 3.75 M, about 4.0 M, about 4.25 M, about 4.33 M, etc. M, approximately 4.5 M, approximately 4.66 M, approximately 4.75 M, approximately 5.0 M, approximately 5.25 M, approximately 5.33 M, approximately 5.5 M, approximately 5.66 M, approximately 5.75 M, approximately 6.0 M, approximately 6.25 M, approximately 6.33 M, approximately 6.5 M, approximately 6.66 M, approximately 6.75 M, approximately 7.0 M, approximately 7.25 M, approximately 7.33 M, approximately 7.5 M, approximately 7.66 M, approximately 7.75 M, approximately 8.0 M, approximately 8.25 M, approximately 8.33 M, approximately 8.5 M, approximately 8.66 M, approximately 8.75 M, approximately 9.0 M, approximately 9.25 M, approximately 9.33 M, approximately 9.5 M, approximately 9.66 M, approximately 9.75 M, or approximately 10 M or any amount between these.

[0037] According to various aspects of the inventive concept now disclosed, performance-enhancing additives include, in any arrangement or combination, acetonitrile, azobisisobutyronitrile (AIBN), cyanamide, lithium dicyandiamide, dicyandiamide (DCDA), guanine, guanidine nitrate, guanidine thiocyanate, guanidine p-toluenesulfonate, guanidine trifluoromethanol, 2-guanidinobenzimidazole, guanidine hydrochloride, guanidine carbonate, guanidine bromide, guanidine iodide, guanidine acetate, guanidine sulfate, guanidine phosphate, succinate, or any suitable equivalent thereof that would come to mind by one of ordinary skill in the art upon reading this disclosure.

[0038] In various embodiments, the performance-enhancing additive may be present in non-zero amounts up to about 0.2 M, for example, ranging from about 0.01 M to about 0.2 M, and preferably in amounts ranging from about 0.1 M to about 0.15 M. Of course, those skilled in the art will realize that the performance-enhancing additive may be present in any amount within the wide range given above, such as about 0.001 M, about 0.005 M, about 0.01 M, about 0.02 M, about 0.05 M, about 0.066 M, about 0.075 M, about 0.09 M, about 0.1 M, about 0.125 M, about 0.133 M, about 0.15 M, about 0.166 M, about 0.175 M, about 0.19 M, about 0.195 M, about 0.199 M, about 0.2 M, or any value or range of values ​​greater than zero to about 0.2 M, and is not limited thereto, unless expressly stated otherwise herein. It should be noted that when the performance-enhancing additive is DCDA, at a level of about 0.2 M or more, the resistance within the electrochemical cell increases dramatically, to the point that the electrochemical cell cannot function properly.

[0039] As noted above regarding solvents and electron-withdrawing compounds, specific performance-enhancing additives included in a given electrolyte system may be selected based on the specific application of the electrochemical cell for which performance-enhancing additives are to be utilized, the composition of other components of the electrolyte system, the composition of other components of the electrochemical cell (such as the anode, cathode, and / or separator), or other factors that a person skilled in the art will understand upon reading this disclosure.

[0040] According to various illustrative embodiments, Table 3 below details the suitable types and amounts of lithium-ion transport compounds and performance-enhancing additives in the exemplary electrolyte system composition.

[0041] Therefore, in the preferred method, the electrolyte system as a whole includes at least one solvent, at least one electron-withdrawing compound, at least one performance-enhancing additive, and at least one lithium-ion transport compound that conform to the parameters given above. Specific combinations of substances or specific combinations of components constituting the aforementioned components can be selected based on various factors, such as the desired performance characteristics of the electrochemical cell to which they are to be implemented (e.g., specific energy, cycle life, power, charge / discharge rate, etc.), the specific application of the electrochemical cell to utilize the electrolyte system, and / or the composition of other components, as well as the composition of other components of the electrochemical cell (e.g., anode, cathode, and / or separator), as described above and as understood by those skilled in the art.

[0042] According to a further embodiment, the electrolyte system can be implemented in an electrochemical single-cell battery including a lithium-based anode. The lithium-based anode preferably includes an interfacial phase formed on its surface, wherein the interfacial phase is formed by the interaction between the active material of the lithium-based anode, performance-enhancing additives and / or solvent derivatives, electron-withdrawing compounds, performance-enhancing additives, or any arrangement or combination thereof.

[0043] The active material of a lithium-based anode preferably contains elemental lithium or a lithium alloy. For example, lithium alloys may include lithium-magnesium, lithium-sulfur, or combinations thereof.

[0044] According to a further embodiment, the electrolyte system can be implemented in an electrochemical single-cell battery including a cathode having a sulfur complex composition. The cathode preferably includes an interfacial phase formed on its surface, wherein the interfacial phase is formed by the interaction between the cathode's active material, performance-enhancing additives and / or solvent derivatives, electron-withdrawing compounds, performance-enhancing additives, or any arrangement or combination thereof.

[0045] According to further embodiments, the electrochemical single cell may include the above-described electrolyte system, anode, cathode, and separator having a composition compatible therewith, as will be understood by those skilled in the art upon reading this disclosure. The electrochemical single cell may be characterized by a coin-shaped structure, a cylindrical structure, a prismatic structure, a pouch structure, or any other suitable construction or arrangement that will occur to those skilled in the art upon reading this specification.

[0046] Further features and advantages of the invention will become apparent upon a thorough reading of the description and accompanying drawings provided herein. It will be understood that, except as expressly stated otherwise in this disclosure, these inventive concepts can be combined in any suitable manner. Therefore, aspects of the invention should be considered modular and can be rearranged, combined, incorporated, or otherwise utilized in any manner that would occur to a person skilled in the art upon reading this disclosure. Furthermore, upon completion of this application, it will be understood by those skilled in the art, within the context of the invention as a whole, that suitable equivalent compounds, formulations, structural arrangements, etc., unless expressly waived to the contrary, are to be construed as part of the invention and not as a limitation. Attached Figure Description

[0047] Figure 1A-1B This is a simplified schematic diagram of the chemical structure of the inventive motif characteristic of the compounds included in the electrolyte system of the present invention described herein, according to various embodiments.

[0048] Figures 2A-1 to 2B-3 This is a simplified schematic diagram of the chemical structure of several exemplary types of selectively β-functionalized compounds of α-hydrogenation according to different methods.

[0049] Figure 3 A simplified schematic diagram of the reaction pathway for the formation of free radicals that promote the conversion of lithium polysulfides from chalcogenide materials according to one embodiment is shown.

[0050] Figures 4A-4E A simplified graph showing the performance characteristics of electrolyte system 401, which includes the electrolyte system of the present invention as disclosed herein and according to one embodiment, and referenced to a control electrolyte system 404, which is otherwise identical to the electrolyte system of the present invention but omits any chalcogenides.

[0051] Figure 4A This is a diagram illustrating the relationship between the discharge capacity and cycle number of the electrolyte system 401 of the present invention and the control electrolyte system 404, according to one embodiment.

[0052] Figure 4B This is a diagram showing the relationship between coulombic efficiency and cycle number for electrolyte system 401 of the present invention and control electrolyte system 404, according to the same embodiment.

[0053] Figure 4C This is a diagram showing the rated capacity of the electrolyte system 401 of the present invention and the control electrolyte system 404 according to the same embodiment.

[0054] Figure 4D This is a diagram showing the relationship between the discharge capacity and the charge rate of the electrolyte system 401 of the present invention and the control electrolyte system 404, according to the same embodiment.

[0055] Figure 4E This is a diagram showing the relationship between potential and capacity of electrolyte system 401 of the present invention and control electrolyte system 404 according to the same embodiment.

[0056] Figure 5A The diagram illustrates the relationship between cycle life and fluoroether concentration for electrolyte systems 401, 411, and 421 of the present invention, and corresponding control electrolyte systems 402, 412, and 422, according to several exemplary embodiments.

[0057] Figure 5B The diagram illustrates the relationship between cycle life and fluoroether concentration for electrolyte systems 401, 411, and 421 of the present invention, and corresponding control electrolyte systems 402, 412, and 422, according to several exemplary embodiments.

[0058] Figures 6A-6D This is a simplified schematic diagram of the chemical structure of a performance-enhancing additive based on several implementation schemes.

[0059] Figure 7AThis is a graph comparing the capacity retention during cycle life of a lithium-sulfur electrochemical cell with a baseline electrolyte composition (control) and a lithium-sulfur electrochemical cell with a baseline electrolyte composition but also including a DCDA additive (+DCDA), according to one embodiment.

[0060] Figure 7B This is a graph comparing the coulombic efficiency of a lithium-sulfur electrochemical cell with a baseline electrolyte composition (control) to a lithium-sulfur electrochemical cell with a baseline electrolyte composition but also including a DCDA additive (+DCDA), according to one embodiment.

[0061] Figure 7C This is a graphic illustration showing the Fourier transform infrared (FTIR) spectra of the solid-electrolyte interface (SEI) of two lithium-sulfur electrochemical single-cell cells (control) with baseline electrolyte composition compared with the SEI of two lithium-sulfur electrochemical single-cell cells (+DCDA) with baseline electrolyte composition but also including DCDA additive, according to one embodiment.

[0062] Figure 8A This diagram shows a simplified schematic cross-sectional view of an electrochemical single-cell battery characterized by a pouch-type single-cell arrangement, according to one embodiment of the currently disclosed inventive concept.

[0063] Figure 8B It is an implementation scheme based on a currently disclosed inventive concept. Figure 8A A simplified schematic external view of the electrochemical single cell shown.

[0064] Figure 8C Describing a method based on a currently disclosed inventive concept. Figure 8B The diagram shows a simplified schematic of a pouch-type single-cell battery arrangement wound into a jelly roll structure.

[0065] Figure 9A This is a simplified schematic diagram of an electrochemical single-cell battery characterized by a coin-cell battery arrangement, based on one embodiment of the currently disclosed inventive concept.

[0066] Figure 9B Depicted according to a simplified schematic exploded view Figure 9A The various components of the coin cell battery arrangement shown are illustrated.

[0067] Figure 10A It is a simplified schematic diagram of an electrochemical single cell battery characterized by a cylindrical single cell arrangement, based on one aspect of the currently disclosed inventive concept.

[0068] Figure 10B This is one implementation method based on the currently disclosed inventive concept. Figure 10AA simplified schematic cross-sectional view of an exemplary component of the cylindrical single-cell battery arrangement shown.

[0069] Figure 11 It is a simplified schematic diagram of an electrochemical single cell battery characterized by a cylindrical single cell arrangement, based on one aspect of the currently disclosed inventive concept.

[0070] Figure 12 It is a diagram showing various forms of carbonaceous materials and methods for preparing them from elemental carbon (e.g., charcoal), which can be included in various components of an electrochemical single-cell battery such as those shown in the foregoing figures. Detailed Implementation

[0071] Further illustrative information will now be provided regarding various optional architectures and uses in which the foregoing methods may or may not be implemented, depending on the user's expectations. It should be emphasized that the following information is given for illustrative purposes and should not be construed as restrictive in any way. Any of the following features may be optionally combined, whether or not other features described are excluded.

[0072] To address the concerns raised above regarding the safety and efficiency of electrolyte systems for lithium-based batteries with suitable performance, a key aspect of the disclosed inventive concept includes an electrolyte system comprising compounds containing building blocks of what is herein termed "α-hydrogenated selective β-functionalized" (or in other words, "α-hydrogenated selective β-functionalized") structures. Preferably, the solvent system is capable of meeting numerous stringent requirements for the aforementioned lithium-based batteries.

[0073] The inventors propose that α-hydrogenated selectively β-functionalized compounds of exemplary class advantageously exhibit similar or better properties because the β position is not sterically hindered in participating in desired chemical reactions (e.g., promoting lithium polysulfide conversion via redox reactions, preferentially forming short-chain lithium polysulfides, robustly forming SEIs, high solvation capability for lithium salts, etc.), while retaining the electron density of the electron-withdrawing group of the α-carbon adjacent to the moiety. As described in more detail below, without such selective β-modification, solvent compounds of moiety that otherwise exhibit similar characteristics (e.g., α-hydrogenated but not β-modified) tend undesirably to decompose into gas in reductive decomposition reaction cascades and eventually evaporate from the solvent system.

[0074] Similarly, the inventive concepts provided herein relate to the use of such electrolyte systems with lithium-based anode materials in electrochemical single-cell batteries. As used herein, the term "lithium-based" should be understood to mean pure lithium metal and lithium alloys or composites (such as Li-Mg, Li-S, Li-C, Li-Al, Li-Fe, and any other suitable equivalents that a person skilled in the art would think of upon reading this specification) or combinations thereof.

[0075] Figure 1A-1B This is a simplified schematic diagram of the chemical structure of the basic units characteristic of the compounds included in the electrolyte system of the present invention described herein, according to various embodiments. Alternatively, it may be implemented within the context of any one or more embodiments given in any of the preceding and / or subsequent figures and / or their descriptions. Figure 1A-1B The basic unit is shown in the diagram. However, the basic unit can, of course, be implemented in any desired environment. For example, solvent systems include amides such as dimethylacetamide (DMA), dimethylformamide (DMF), or any other suitable equivalent thereof that will come to mind by one of ordinary skill in the art upon reading this disclosure. Furthermore, the foregoing definitions are equally applicable to the description below.

[0076] like Figure 1A As shown, the basic unit typically includes α-carbon (C). α It is hydrogenated (i.e., has at least one hydrogen bonded to it, preferably saturated with hydrogen, and more preferably not directly bonded to another electron-withdrawing group other than X), and directly bonded to β-carbon C. β It is bonded to an electron-withdrawing group X. According to various embodiments, the electron-withdrawing group is characterized by having an electronegativity greater than that of carbon, and preferably by having an electronegativity greater than that of the α-carbon bonded to X. Preferably, X is not a halogen. Therefore, in a preferred embodiment, X may be selected from nitrogen, oxygen, and sulfur.

[0077] Continue to refer to Figure 1A In C α In the implementation scheme that is not saturated with hydrogen, C α It can bond with X double bonds, such as in terminal aldehydes, where C α It is bonded to a single hydrogen atom and to a double bond of X, where X is oxygen.

[0078] Besides with α-carbon C α In addition to bonding, β-carbon C βIt is also bonded to the modifying group Y and the aliphatic or aromatic side chain R. Whether R is aliphatic or aromatic, a shorter chain (e.g., C1-C20) is preferred to minimize the total mass of the molecule. Furthermore, in various embodiments, the backbone of R may include elements other than carbon, including but not limited to phosphorus, sulfur, oxygen, nitrogen, etc., as will be apparent to those skilled in the art upon reading this disclosure. In some methods, R may be functionalized, such as with halogens, amines, amides, oxides, thiols, etc., as will be understood by those skilled in the art upon reading this disclosure.

[0079] Optionally, depending on the specific types of Y and R and β-carbon C β The bond between Y and R, β carbon C β It can be optionally bonded to hydrogen (not shown) or to a Y or R double bond.

[0080] according to Figure 1A In the implementation scheme described herein, the electron-withdrawing group X is a terminal functional group of a molecule containing a selectively β-functionalized α-hydrogenated moiety.

[0081] Of course, in alternative implementation schemes, such as Figure 1B As shown, the electron-withdrawing group X can be part of the main chain of the molecule, such as for secondary or tertiary amines (where X is nitrogen), ethers (where X is oxygen), or organic sulfur (where X is sulfur), as would be apparent to a person skilled in the art upon reading this specification.

[0082] Continue to refer to Figure 1B And in addition to what has just been pointed out above, regarding... Figure 1A The C mentioned α C β The bonding of Y and R and the consideration of the same specific type apply to, for example, Figure 1B The primitives shown. Furthermore, regarding C... α’ C β’ Similar considerations apply to Y' and R', except that in some arrangements, R and R' can be part of the same aromatic structure that links molecules into a ring (or polycyclic) structure. For example, see the following section on... Figure 2B-3 In more detail, R and R' can form a connected double-ring structure. Of course, it will be understood that, depending on the various implementation schemes, C α C β Y, R, C α’ C β’ Y' and R' can each be defined independently based on any suitable combination of the features (specific types, bonding, etc.) described above.

[0083] Figures 2A-1 to 2A-3This is a simplified schematic diagram of the chemical structures of several exemplary types of selectively β-functionalized α-hydrogenated compounds, where the β-modification is fluorine (i.e., Y = F), and Figure 2B-3 An exemplary α-hydrogenated selectively β-functionalized compound is described, wherein, depending on the method, the β-modification is not fluorine (i.e., Y = ONO2). Alternatively, the exemplary compound may be implemented in the context of any one or more embodiments given in any of the preceding and / or subsequent figures and / or their descriptions. However, the compound may certainly be implemented in the context of any desired environment. Furthermore, the foregoing definitions are equally applicable to the description below.

[0084] like Figure 2A-1 , 2A-2 As shown in 2A-3, the exemplary electron-withdrawing compounds (1,1,1-trifluoro-2,3-dimethoxypropane (TFDMP), 4-(trifluoromethyl)-1,3-dioxolane (TFDOL), and (3-fluoropyridine) (3F-P) respectively) conform to Figure 1A The primitive shown. In Figure 2A-3 In the formation of R and C α Aromatic rings connected by a foldback. For Figure 2A-1 and 2A-2 In the structure shown, X is oxygen, and for Figure 2A-3 In the structure shown, X is nitrogen.

[0085] Figure 2B-1 , 2B-2 It conforms to the exemplary electron-withdrawing compounds shown in 2B-3 (bis(2-fluoroethyl) ether (BFE), bis(2,2,2-trifluoroethyl) ether (BTFE), and isosorbide dinitrate (ISDN), respectively). Figure 1B The primitive shown. For Figure 2B-1 , 2B-2 And in the electron-withdrawing compounds shown in 2B-3, X is oxygen. For Figure 2B-1 and 2B-2 In the electron-withdrawing compound shown, Y is fluorine. (Only for...) Figure 2B-3 The electron-withdrawing compound shown is Y, which is ONO2.

[0086] certainly, Figures 2A-1 to 2B-3 The exemplary structures shown are to be understood as illustrating the scope of electron-withdrawing compounds according to various embodiments of the inventive concept provided herein. According to different embodiments, including Figure 1AOther compounds of the motifs shown in 1B may also be suitable electron-withdrawing compounds, as detailed below with reference to Table 2. In particular, without departing from the scope of the inventive concept given herein, exemplary suitable electron-withdrawing compounds such as 2,2-dimethoxy-4-trifluoromethyl-1,3-dioxolane (DTDL), 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG), and 1,1,1,1,14,14,14-hexafluoro-3,6,9,12-tetraoxatetradecane (FTrG) may be used as electron-withdrawing compounds. ), 1,1,1,17,17,17-hexafluoro-3,6,9,12,15-pentaheptadecane (FTeG), bis(2,2-difluoroethyl) ether (BDE), 2,2,2-trifluoroethyl 2-fluoroethyl ether (TFFE), 1,1-difluoroethyl-2-fluoroethyl ether (DFE), fluorinated 1,4-dimethoxybutane (FDMB), 1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,3,3-tetrafluoropropyl) ether (BTFPE), 2,2,2-trifluoroethyl 1,1,2,2-tetrafluoroethyl ether (TFTFE), tris(2,2,2-trifluoroethyl) phosphate, bis(2,2,2-trifluoroethyl) methylphosphonate, or other suitable equivalents and combinations thereof that will come to mind by one of ordinary skill in the art upon reading this disclosure. Furthermore, combinations of electron-withdrawing groups may be employed without departing from the scope of the inventive concept described herein.

[0087] Furthermore, those skilled in the art will recognize, such as Figure 2B-3 The compounds shown that do not contain any fluorine or other halogens are particularly preferred types of electron-withdrawing compounds because they do not cause the environmental problems associated with heavily halogenated, especially heavily fluorinated, compounds. In fact, according to certain methods, the exemplary electron-withdrawing groups discussed above, their analogues, and / or derivatives thereof can be modified to replace halide functional groups with -ONO2 functional groups, thereby forming nitrate esters and mitigating or eliminating the environmental problems associated with PFAS and other so-called "permanent chemicals."

[0088] Similarly, in a particularly preferred embodiment, the electrolyte solvent system of the present invention may include lithium salts that do not contain any halogen components, such as LiClO4, or other suitable equivalents (and combinations thereof) that will come to mind by one of ordinary skill in the art upon reading this disclosure.

[0089] Furthermore, in the context of the present invention, the preferred electron-withdrawing compounds are characterized by having the shortest possible R and / or R' groups, again in order to minimize the mass contribution of the electron-withdrawing compounds to the overall electrolyte system and to the electrochemical cell comprising such electrolyte systems.

[0090] Figure 3 A simplified schematic diagram of the reaction pathway for the formation of free radicals that promote the conversion of lithium polysulfides from chalcogenide materials according to one embodiment is shown.

[0091] Figures 4A-4E A simplified graph showing the performance characteristics of electrolyte system 401, which includes the electrolyte system of the present invention as disclosed herein and according to one embodiment, and referenced to a control electrolyte system 402, which is otherwise identical to the electrolyte system of the present invention but omits any chalcogenides.

[0092] Figure 4A This is a diagram illustrating the relationship between the discharge capacity and cycle number of the electrolyte system 401 of the present invention and the control electrolyte system 402, according to one embodiment.

[0093] Figure 4B This is a diagram showing the relationship between coulombic efficiency and cycle number for electrolyte system 401 of the present invention and control electrolyte system 402, according to the same embodiment.

[0094] Figure 4C This is a diagram showing the rated capacity of the electrolyte system 401 of the present invention and the control electrolyte system 402 according to the same embodiment.

[0095] Figure 4D This is a diagram showing the relationship between the discharge capacity and charge / discharge rate of the electrolyte system 401 of the present invention and the control electrolyte system 402 according to the same embodiment.

[0096] Figure 4E This is a diagram showing the relationship between the potential and capacity of the electrolyte system 401 of the present invention and the control electrolyte system 402 according to the same embodiment.

[0097] The electrolyte system 401 of this invention and the control electrolyte system 402 each comprise, in equal amounts, two solvents, an electron-withdrawing compound, and two lithium-ion transport compounds. The electrolyte system 401 of this invention further comprises approximately 1% by weight of the chalcogenide DMDSe.

[0098] Depend on Figures 4A-4E It can be seen that, compared with the control electrochemical single cell 402, the electrolyte system 401 of the present invention exhibits a more significant response to Li2S. (s)The presence / generation of features. Furthermore, the capacity of the electrochemical single-cell battery 401 of the present invention reversibly increases at each rate. Not wishing to be bound by any particular theory, the inventors propose that the improved performance of the electrochemical single-cell battery of the present invention may be at least partially attributed to the increase in capacity through the second discharge plateau, due to the improved liquid-solid reaction kinetics of polysulfide conversion (Equation 1(c) above).

[0099] Similar experiments with a second inventive electrolyte system 403, which uses the same formulation as the electrolyte system 401 of the present invention but includes DPDSe instead of DMDSe as a chalcogenide component, showed improved performance relative to the control electrolyte system 402, but was inferior to the electrolyte system 401 of the present invention in all metrics. Again, not wanting to be bound by any particular theory, the inventors propose that DPDSe contributes to the kinetics of liquid-liquid conversion reactions (Equations 1(a)-1(b)) that are not rate-limiting steps, until the larger barrier presented by the liquid-solid conversion (Equation 1(c)) is removed and mitigated by the inclusion of DMDSe.

[0100] In further experiments, the inventors varied the amount of DMDSe in the electrolyte system 401 of the present invention, and tested embodiments including 0.5 wt% DMDSe, 1.0 wt% DMDSe and 2.0 wt% DMDSe, but otherwise identical to the formulation described above for the electrolyte system 401 of the present invention.

[0101] While further performance improvements were expected with increasing DMDSe concentrations above 1 wt%, the opposite relationship was observed, with significant losses in discharge capacity, coulombic efficiency, and rated capacity at concentrations greater than 1 wt%. Although improvements in lithium polysulfide conversion kinetics were anticipated with a greater number of available radicals (i.e., higher concentrations of DMDSe), the inventors presume that when included at approximately 1 wt%, the increased DMDSe achieves the best improvement in liquid-solid (and, to a lesser extent, solid-solid) reaction kinetics, reaching a point where it is no longer the rate-limiting step in the overall pathway. Above this concentration, lithium polysulfide shuttle may increase, but without any corresponding benefit to discharge capacity. In other words, including DMDSe as a chalcogenide improves the kinetics of the lower plateau (liquid-solid reaction), while including DMDSe improves the kinetics of the higher plateau (solid-liquid reaction). When the electrolyte system includes certain electron-withdrawing compounds (such as BTFE) that independently contribute to the reaction entering the liquid state, the addition of chalcogenides that promote the liquid-solid reaction provides a synergistic improvement to the overall lithium polysulfide conversion, thereby increasing the sulfur utilization rate in the resulting electrochemical single cell.

[0102] The above is just one example of the observations above, namely that the composition of a particular electrolyte system does not necessarily follow the usual trends and expectations regarding reaction kinetics and corresponding performance characteristics.

[0103] In further experiments, the inventors tested a formulation of the electrolyte system of the present invention that is similar to electrolyte system 401 of the present invention, but includes a combination of equal amounts of DMDSe and DPDSe, each at 0.5 wt% and 1.0 wt%, respectively, because these concentration ranges produce optimal results for similar electrolyte systems of the present invention, as referenced in [reference]. Figures 4A-4E As shown and described above.

[0104] Generally, mixed diselenide electrolyte formulations show little difference in cycle life and a slight improvement in capacity and coulombic efficiency at a 1 wt% concentration, although lower coulombic efficiency is expected due to the presence of more selenide (i.e., the system including 1 wt% DMDSe and DPDSe respectively is comparable to the system including 2 wt% DMDSe in terms of selenide concentration, while the latter is observed to have poorer coulombic efficiency relative to 1 wt% DMDSe alone, but the combination of 1 wt% DMDSe and DPDSe respectively does not show the same loss, and in fact a slight increase is observed).

[0105] In addition to testing different types of chalcogenides, the inventors also studied different concentrations of electron-withdrawing compounds (especially hydrofluoroethers TTE, BTFE, or FDMB) in the formulation, which in other respects is similar to the formulation described above. Figures 4A-4E The electrolyte system 401 of the present invention shown and described herein.

[0106] The results of these experiments are summarized in Table 1 and... Figures 5A-5B middle.

[0107] Table 1: Relationship between lithium-based battery performance and hydrofluoroether composition It should be noted that the capacities shown in Table 1 are based on electrodes, not on sulfur reports.

[0108] Figures 5A-5B Exemplary curves are depicted for the electrolyte systems 401, 411, and 421 of the present invention, and the corresponding control electrolyte systems 501, 511, and 521. According to Table 1, each electrolyte system comprises, in the same amounts within the scope described herein, two solvents, one electron-withdrawing compound (BTFE for electrolyte systems 401 and 501, FDMB for electrolyte systems 411 and 511, and TTE for electrolyte systems 421 and 521, respectively), two lithium-ion transport compounds (LITFSI and LiNO3), and a chalcogenide component (DMDSe).

[0109] Figure 5A The relationship between the performance of a single battery cell in terms of cycle life (defined by these experiments as retaining at least 80% of its capacity after discharge) and the concentration of hydrofluoroether is depicted. Figure 5B The relationship between capacity performance and hydrofluoroether concentration is described.

[0110] As briefly mentioned above, testing different hydrofluoroethers and their concentrations yielded unexpected results that did not follow conventional knowledge about the role of hydrofluoroethers (and indeed, often fluorine) in lithium-based batteries. Generally, the addition of fluorine to the electrolyte system of a lithium-based battery is associated with an increase in the cycle life of the resulting battery. This is because the conventional understanding is that added fluorine corresponds to reduced solubility and (typically concentrated and highly viscous) electrolyte wettability on electrode surfaces.

[0111] Furthermore, hydrofluoroethers and similar electron-withdrawing compounds are conventionally understood (and actually designed) to be inert to both electrodes of lithium-based batteries. Moreover, for lithium-sulfur battery chemistry, there are strict limitations on the amount of salts that can be included due to their limited solubility in the remaining components of the electrolyte system and in the battery as a whole.

[0112] The presently disclosed inventive concept uses these electron-withdrawing compounds in electrolytes with low salt concentrations because of their low Lewis acid-base interaction with polysulfides (low solubility), and because it was previously assumed that these compounds, in particular hydrofluoroethers, are "known" inert to lithium-based anode materials known for their reactivity.

[0113] The presently disclosed inventive concept uses these electron-withdrawing compounds in electrolytes with low salt concentrations because of their low Lewis acid-base interaction with polysulfides (low solubility), and because it was previously assumed that these compounds, in particular hydrofluoroethers, are "known" inert to lithium-based anode materials known for their reactivity.

[0114] Figures 6A-6D This is a simplified schematic diagram of the chemical structure of the performance-enhancing additive according to several implementation schemes. According to the illustrative implementation scheme, Figure 6A The structure of dicyandiamide is shown, and Figure 6B Showing the structure of guanine, Figure 6C The chemical structure of guanidine nitrate is shown, and Figure 6D Describe the chemical structure of lithium dicyandiamide.

[0115] Without being bound by any particular theory, the inventors propose that the electrolyte system of the present invention forms a protective solid-electrolyte interface (SEI) on the surfaces of both the cathode and anode of the lithium-based electrochemical single cell in which the electrolyte system is introduced.

[0116] For details on the contribution of solvents and electron-withdrawing compounds to the SEI, see U.S. Provisional Patent Application No. 63 / 624,202 and subsequent applications for a detailed study and discussion of the mechanism and chemical structure of the resulting SEI components.

[0117] Regarding performance-enhancing additives, again not wanting to be bound by any particular theory, the inventors propose that suitable additives, such as acetonitrile, azobisisobutyronitrile (AIBN), cyanamide, lithium dicyandiamide, dicyandiamide (DCDA), guanine, guanidine nitrate, guanidine thiocyanate, guanidine p-toluenesulfonate, guanidine trifluoromethanol, 2-guanidinobenzimidazole, guanidine hydrochloride, guanidine carbonate, guanidine bromide, guanidine iodide, guanidine acetate, guanidine sulfate, guanidine phosphate, succinate, or any combination thereof, form a protective thin film polymer on or around the electrode surface. This protective film mitigates the well-known polysulfide shuttle effect and its adverse effects, and protects the anode, especially from delithiation (stripping), during the cycling of electrochemical single cells.

[0118] Therefore, and as Figures 7A-7B The data shown reflects the cycle life of lithium-based electrochemical single-cell batteries implementing the electrolyte system of the present invention. Figures 7A-7B ) and Coulomb efficiency ( Figure 7B All of them improved significantly.

[0119] For example, refer to again Figures 7A-7B It is evident that the control electrochemical single cell (control, circular data point), which includes an electrolyte system without any performance-enhancing additives, experiences a sharp decrease in coulombic efficiency after about 90 cycles and fails after about 100 cycles.

[0120] In contrast, lithium-based electrochemical single-cell batteries incorporating the electrolyte system of the present invention exhibit significantly improved coulombic efficiency retention, maintaining above 80% after 225 cycles. In fact, selected embodiments of lithium-based electrochemical single-cell batteries implementing the electrolyte system of the present invention, as disclosed herein, retain activity (above 80% CE) after 300 cycles.

[0121] It is important to note, and especially as Figure 7A As shown, these benefits are not related to a loss of specific capacity, which remains similar to that of the control, and are stable over the long cycle life of the electrochemical single cell of the present invention.

[0122] In addition, it is used to generate Figures 7A-7BThe electrochemical single-cell battery implementations shown in the comparative data are charged and discharged at a rate of C / 3, but other implementations exhibit similar performance characteristics when charged at a rate of up to about 1C, indicating that the electrolyte system of the present invention described herein can also facilitate higher charge / discharge rates (e.g., about C / 3) than can typically be achieved using similar electrochemical single-cell batteries without the electrolyte system of the present invention described herein.

[0123] Figure 7C This is a graphic illustration showing the Fourier transform infrared (FTIR) spectra of the solid-electrolyte interface (SEI) of two lithium-sulfur electrochemical single-cell batteries (control) with baseline electrolyte composition, compared with the SEI of two lithium-sulfur electrochemical single-cell batteries (+DCDA) of the present invention, which also include DCDA additive, according to one embodiment.

[0124] As is evident from the spectrum, the SEI of the electrochemical single-cell battery of this invention exhibits two distinct peaks, 702a and 702b, in the wavelength range of 2000-2200 nm. Without wishing to be bound by any particular theory, the inventors presume that these peaks correspond to the presence of lithium cyanide and lithium thiocyanate in or on the SEI. These compounds are believed to be formed by the concerted decomposition of DCDA at the electron-donating anode in the presence of oxidizing agents such as polysulfides and nitrates.

[0125] Furthermore, given the double-ended nature of cyanate and thiocyanate anions—each possessing an "anion" end with a Lewis basic negative charge and a Lewis basic nitrogen atom with a lone pair of electrons at the other end—the inventors propose that these substances enhance the Li… + Transmission, and / or addition of Li in SEI + The concentration of these compounds favorably enhances the robustness of the interfacial phase against degradation and correspondingly extends the cycle life of the electrochemical single-cell battery. In other words, cyanate and thiocyanate promote the degradation of Li. + Ion transport without (or at least significantly less) causing SEI degradation, thus allowing Li to be present in the single cell. + It is designed specifically for normal cycling rather than SEI reconstruction. This mechanism is particularly effective in later cycles, thus significantly extending the lifespan of electrochemical single-cell batteries.

[0126] Although Figures 6-7C and the corresponding descriptions above feature that the electrolyte system of the present invention includes one or more compounds selected from acetonitrile, azobisisobutyronitrile (AIBN), cyanamide, lithium dicyandiamide, dicyandiamide (DCDA), guanine, guanidine nitrate, guanidine thiocyanate, guanidine p-toluenesulfonate, guanidine trifluoromethanol, 2-guanidinobenzimidazole, guanidine hydrochloride, guanidine carbonate, guanidine bromide, guanidine iodide, guanidine acetate, guanidine sulfate, guanidine phosphate, succinate, or any combination thereof as performance-enhancing additives, those skilled in the art will, upon reading this specification, realize that other suitable equivalents thereof may be implemented as performance-enhancing additives in any suitable arrangement, combination, or amount without departing from the scope of the inventive concept disclosed herein.

[0127] For example, derivatives of performance-enhancing additives, isomers of performance-enhancing additives, compounds having similar chemical motifs and / or structures, and larger molecules including performance-enhancing additives or substantially similar structures as part of a larger molecular structure can be implemented as performance-enhancing additives, while still remaining within the scope of the inventive concept given herein.

[0128] Alternatively, in the context of the presently disclosed inventive concept, a compound capable of forming a thin-film protective polymer layer having a composition similar to that of a thin film formed by a performance-enhancing additive or its derivatives (alone or in combination with other components of an electrolyte system in various methods) can be used as a performance-enhancing additive.

[0129] Tables 2 and 3 below summarize, respectively, various suitable compositions of the solvent system and other components of the electrolyte system of the present invention described above, based on several exemplary embodiments. It will be understood that the exemplary embodiments given in the tables are provided by way of illustration rather than limitation, and other compositions within the scope of the disclosure provided herein may be employed without departing from the scope of the inventive concept set forth herein.

[0130] Furthermore, for the sake of brevity and simplicity of structure, these tables describe different components and appropriate amounts individually and in selected combinations. However, it will be understood that, without departing from the scope of the inventive concept described herein, any combination of different substances in appropriate amounts can be used within the wide range given above.

[0131] For example, any number of different types of solvents, electron-withdrawing compounds, lithium-ion transport compounds, and / or performance-enhancing additives can be included in the electrolyte system composition, with the only limitation being that the total amount of solvents, electron-withdrawing compounds, lithium-ion transport compounds, and performance-enhancing additives falls within the wide range given above for their respective components.

[0132] Table 2: Components of Exemplary Solvent Systems Table 3: Exemplary Additional Components In various methods, the structures, compositions, and configurations of the present invention described herein can be implemented in various types of electrochemical single-cell batteries for practical use in a wide range of applications. Without limitation, exemplary electrochemical single-cell battery configurations utilizing any combination of the features described herein can take the form of pouch cells, coin cells, prismatic single-cell batteries, cylindrical configurations, or any suitable equivalent that would occur to a person skilled in the art upon reading this disclosure.

[0133] Referring to an electrochemical cell with a pouch-type single-cell arrangement of 800, and as according to Figures 8A-8C As shown in the exemplary embodiment, the electrochemical single cell includes a cathode 810a and an anode 810b located on opposite sides of a pouch cell arrangement 800 and separated (physically and / or chemically) by a separator 810c. The anode 810c and cathode 810a are electronically coupled via an electrolyte 810f present in the pouch cell arrangement 800. Furthermore, each electrode is electronically coupled to the external environment of the pouch cell arrangement 800 via a current collector and a corresponding terminal; that is, the cathode 810a is coupled to the external environment via a cathode current collector 810d and a cathode terminal 806a, while the anode 810b is coupled via an anode current collector 810e and an anode terminal 806b. The aforementioned structure is enclosed, contained, or otherwise spatially fixed and housed by a pouch 802 surrounding the component.

[0134] According to various embodiments, bag 802 may take any suitable form that a person skilled in the art would understand upon reading this disclosure, such as wrapping material, coating, shell (soft or hard), compression structure (such as metal strip or mesh), etc., as a person skilled in the art would understand upon reading this disclosure.

[0135] In addition, such as Figure 8B As shown, the anode terminal 806b and cathode terminal 806a extend through the pouch 802, thereby providing electronic coupling between the internal and external environments of the pouch cell arrangement 800. It should be noted that the anode terminal 806b may alternatively be located on the same side or opposite side of the pouch cell arrangement 800 relative to the cathode terminal 806a. Furthermore, according to alternative embodiments, and without departing from the scope of the inventive concept described herein, the relative positions of the anode terminal 806b and cathode terminal 806a may be relative to... Figure 8B and 8C The arrangement shown is changed.

[0136] like Figure 8A and 8B As shown, the illustrative pouch cell arrangement 800 can be wound around, for example, its longitudinal axis to form a spiral, folded, pleated, coiled, or otherwise at least partially overlapping configuration of the electrochemical cell components mentioned above. In a preferred embodiment, the wound pouch cell arrangement 800 is formed in... Figure 8C The diagram illustrates the structure known as a "jelly roll".

[0137] Turn now Figure 9A and 9B They depict simplified schematic diagrams of electrochemical single-cell cells constructed according to a coin-shaped single-cell cell arrangement 900, because they are like... Figure 9A It is named for its generally flat cylindrical shape as shown. According to various embodiments, the cylindrical single cell arrangement 900 includes a housing 902 and a cover 904, the latter protecting the components placed therein from mechanical damage, chemical damage (e.g., corrosion, oxidation, etc.), electrical damage, etc., and preventing compounds within the cylindrical single cell arrangement 900 from leaking into the environment.

[0138] The anode terminal 906b is coupled to the cover 904, and similarly, the cathode terminal 906a is coupled to the housing 902. Figure 9B (Not shown in the text). Preferably, these terminals have a composition suitable for conducting electricity generated within the coin cell battery arrangement 900 to a properly connected or coupled output, and can be inserted into a circuit to provide power thereto, as would be apparent to a person skilled in the art upon reading this specification. Exemplary compositions suitable for the cathode terminal 906a and anode terminal 906b include conductive metals such as copper, nickel, etc., known in the art; conductive carbonaceous materials such as graphene, etc., known in the art; or any other suitable equivalent that would be apparent to a person skilled in the art upon reading this disclosure.

[0139] Turn now Figure 9BAn exploded view, consistent with various embodiments of the inventive concept now described, shows several components that may be included in the coin cell battery arrangement 900. It is to be understood that components such as washers / springs 920, spacers 922, and gaskets 924, indicated by dashed outlines, are optional and may, but are not required, to be included according to the inventive concept disclosed herein. However, it will also be understood that, depending on the intended application of the coin cell battery arrangement 900, washers / springs 920, spacers 922, and / or gaskets 924 may advantageously provide mechanical strength or favorable electrical characteristics to the coin cell battery arrangement 900. For example, washers / springs 920 and / or gaskets 924 may help secure other depicted components in place, facilitating the desired operation of the coin cell battery arrangement 900. Similarly, according to Figure 9B As shown in the configuration, the spacer 922 can buffer the anode 910b from frictional or compressive forces from the washer / spring 920, and / or is formed of a material that facilitates the conduction of heat and / or electricity from the interior of the coin cell arrangement 900 to the anode terminal 906b. Of course, based on the knowledge generally available at the time of filing of this disclosure, those skilled in the art will appreciate that various advantages can be achieved by including the washer / spring 920, the spacer 922, and / or the gasket 924 in various embodiments.

[0140] Continue to refer to Figure 9B The illustrative coin cell arrangement 900 is characterized by its internal components including an anode 910b disposed opposite the cathode 910a of the coin cell arrangement, a separator 910c, and an electrolyte 910f disposed therebetween. (As...) Figure 8A-11 All electrochemical cell arrangements shown herein, and consistent with their corresponding descriptions provided herein, may each feature an anode 910b, cathode 910a, separator 910c, and electrolyte 910f as any composition known in the art or described herein, which, upon reading this disclosure, will lead one to realize that these compositions are suitable for their respective functions in the electrochemical cell without departing from the scope of the inventive concept now described. Several such exemplary compositions are provided below, and other compositions may be given elsewhere in the detailed description of the inventive concept given herein. Except as expressly acknowledged as known in the art, it will be understood that any such exemplary compositions described for any component of the electrochemical cell arrangements 8A-11 are not considered so well-known, but are considered to be part of the inventive concept given herein.

[0141] In other methods, electrochemical single-cell cells can be characterized by an arrangement of 1000 cylindrical single-cell cells, for example, according to... Figure 10A The illustrative embodiments shown in (external view) and 10B (sectional view) include a housing 1002 and a cover 1004, which are arranged in accordance with the coin cell battery arrangement described herein (e.g. Figure 9Aand 9B The coin-shaped single-cell battery arrangement 900 shown in the illustration houses and protects other components within the cylindrical single-cell battery structure in a manner similar to that described herein. Also similar to other arrangements described herein, according to various embodiments and as will be apparent to those skilled in the art upon reading this disclosure, the cover 1004 and housing 1002 each include terminals configured to conduct electricity generated within the cylindrical single-cell battery arrangement 1000 to the external environment, output devices electrically coupled to the cylindrical single-cell battery arrangement 1000, etc. Figure 10B As shown, cover 1004 includes cathode terminal 1006a, while housing 1002 includes anode terminal 1006b substantially disposed at opposite ends of the cylindrical single-cell arrangement 1000. Figure 10B (Not shown in the image). Of course, according to an alternative embodiment of the cylindrical single cell arrangement 1000, the relative positions of the cathode terminal 1006a and the anode terminal 1006b can be interchanged.

[0142] Continue to refer to Figure 10B The illustrative cylindrical cell arrangement 1000 includes components similar to those described herein with reference to other electrochemical cell arrangements, but arranged in a structurally unique manner. Most notably, although the cathode 1010a and anode 1010b are spatially separated by a separator 1010c, multiple such structures are arranged in a substantially layered configuration and wound around the central longitudinal axis of the cylindrical cell arrangement 1000. In this way, the cathode 1010a and anode 1010b are not located close to opposite ends of the cylindrical cell arrangement 1000 as in the cases of the pouch cell arrangement 800 and the coin cell arrangement 900, but rather exist throughout the entire volume of the cylindrical cell arrangement 1000. However, consistent with the pouch cell arrangement 800, the cylindrical cell arrangement 1000 includes a cathode current collector 1010d (… Figure 10B (Not shown in the diagram) and anode current collector 1010e, which are disposed at opposite ends of the cylindrical single cell arrangement 1000 and electrically coupled to corresponding terminals (i.e., cathode terminal 1006a or anode terminal 1006b), as will be understood by one of ordinary skill in the art upon reading this disclosure.

[0143] See now Figure 11 This diagram shows a simplified schematic of an electrochemical single-cell battery implemented with a prismatic structure 1100 according to one aspect of the now-disclosed inventive concept. Like other electrochemical single-cell battery arrangements described above, the prismatic single-cell battery arrangement 1100 includes a housing 1102 and a cover 1104. The prismatic single-cell battery arrangement 1100 is unique in that, as... Figure 11The housing 1102 and cover 1104 shown are substantially rectangular cubes in shape, but those skilled in the art will appreciate that a unique advantage of the prismatic single-cell arrangement envisioned herein is the virtually limitless flexibility in the spatial configuration of the housing 1102 and cover 1104. The only limitation to this spatial configuration is the ability to completely enclose and accommodate the internal components, as shown in an exemplary embodiment of the reference electrode and separator arrangement 1110. This flexibility is largely due to the implementation of the electrode and separator arrangement 1110, characterized by a layered structure comprising an anode 1110a and a cathode 1110a physically and / or chemically separated by separators 1110c. Although Figure 11 The specific electrode and separator arrangement 1110 shown is a multilayer structure (e.g., consisting of a series of thin films sequentially deposited on one another), but those skilled in the art will understand that, according to various embodiments, the components of the electrode and separator arrangement 1110 (which may include components other than the anode 1110b, cathode 1110a, and separator 1110c without departing from the scope of the inventive concept disclosed herein) can be constructed in a “rolled-up” manner (e.g., Figure 8C and 10B (as shown) or any other structural arrangement in which at least portions of the components of the electrode and separator arrangement 1110 overlap themselves, each other, or both themselves and each other at least partially. Furthermore, combinations of overlapping arrangements may be implemented in the electrode and separator arrangement 1110 without departing from the scope of the inventive concept now disclosed.

[0144] Return to Figure 11 The exemplary prismatic single-cell battery arrangement 1100 shown in the illustration has a cover 1104, in one illustrative embodiment, with a plurality of terminals, including a cathode terminal 1106a and an anode terminal 1106b, disposed on the outer surface of the cover 1104, and via one or more current collectors, for example, using any suitable means and / or mechanism that a person skilled in the art will understand after reading this specification. Figure 11 (Not shown in the image) is electrically coupled to the electrode and separator arrangement 1110.

[0145] Already referenced Figure 8A-11 Several exemplary electrochemical single-cell battery arrangements have been shown and described, and should be understood as illustrative rather than limiting of the scope of the inventive concept presented herein. Furthermore, some arrangements are depicted as including or omitting certain components not explicitly shown or described with reference to other arrangements, such as those referenced in… Figure 8A Washers / springs 820, spacers 822, gaskets 824, electrolytes 810f, current collectors 810d and 810e are shown but not explicitly shown or described in reference to other arrangements given herein. Although Figure 8A-11Specific components are shown, but it will be understood that any electrochemical single-cell battery arrangement, regardless of its configuration, is possible. Figure 8A-11 Depending on the different electrochemical cell arrangements, any suitable combination of components described with reference to any single figure or components not shown in any figure but which a person skilled in the art would conceive of after reading this specification as suitable for manufacturing a functional electrochemical cell may be included.

[0146] Of course, according to Figure 8A-11 The various exemplary embodiments of the electrochemical single-cell batteries with different construction arrangements shown and described above are provided for illustrative purposes and should not be construed as limiting the scope of electrochemical single-cell batteries in which the anode structures and compositions of the present invention, now disclosed, can be implemented. For example, in various approaches, different electrochemical single-cell battery constructions can be used in arbitrary combinations to provide power to one or more machines.

[0147] Furthermore, the exemplary electrochemical cell structure described above can be modified in any suitable manner known in the art without departing from the scope of the inventive concept described herein. For example, the above-described exemplary electrochemical cell structure can be modified in any manner suitable for manufacturing a working electrochemical cell as would be conceived by a person skilled in the art upon reading this disclosure, without exceeding the scope of the inventive concept now described. Figure 8A-11 The various components shown can be modified, replaced, omitted, or supplemented.

[0148] For example, according to various embodiments, an electrochemical single cell implemented according to the inventive concept described herein may include one or more (preferably at least two) electrodes, which may be individually characterized as an anode or cathode, for example, depending on the electrochemical function within the entire single cell, and may be formed from any suitable material known in the art and conceivable upon reading this disclosure as suitable for use in conjunction with other structures and compositions in exemplary electrochemical single cells according to the inventive concept provided herein.

[0149] In some methods, one or two electrode types can be configured as a “self-supporting” three-dimensional monolithic structure. In other words, a “self-supporting” electrode is “structurally self-supporting” such that when deposited, positioned, or otherwise placed in an operating environment (such as an electrochemical single-cell battery), the monolithic material does not require a separate substrate, frame, support, foam, matrix, current collector, support fluid, etc., to support its own weight and maintain defined physical characteristics (e.g., density, volume, porosity, physical dimensions, shape, chemical composition, etc.). Of course, the inventive concepts presented herein should not be construed as limiting in any way to including or requiring “self-supporting” electrodes, but should be understood as permissible where such structures are advantageous to a particular application or the intended use of the electrochemical single-cell battery of interest.

[0150] When implementing a "self-supporting" electrode structure, depending on the selected embodiment, the corresponding electrochemical cell may, and preferably certainly does, omit different current collectors (or at least different anode current collectors). Indeed, even in the absence of a "self-supporting" electrode structure, the electrochemical cell according to the inventive concept described herein can still omit different current collector structures or components.

[0151] For example, according to some embodiments, the electrode itself may serve as a current collector, or the separator may serve as a current collector in addition to fulfilling the other functions described herein, such as separating the various components of an electrochemical cell in a physical, chemical, or electrical manner to avoid undesirable chemical reactions, physical phenomena, etc., as will be understood by one of ordinary skill in the art upon reading this disclosure. Furthermore, according to various embodiments, the inventive concept presented herein will be understood to include, but not require, the omission of different current collector components.

[0152] Therefore, the electrodes of the illustrative electrochemical single-cell battery embodiments can have different structures, such as three-dimensional monolithic materials, which may optionally be porous, with surfaces functionalized to enhance, suppress, or otherwise modify their functional properties (such as permeability, reactivity, etc., to selected chemical substances present within the electrochemical single-cell battery), but are not limited thereto. Electrodes may optionally include indeterminate structures, such as solutions exhibiting the functional properties of a monolithic electrode structure but present partially or entirely in solution form. Furthermore, electrodes can be sprayed or deposited according to various structural physics, such as thin films that can be sprayed or deposited on suitable substrates; one or more (flat) layers that can be sprayed or deposited on suitable substrates or as self-supporting structures; as multiple rows and / or trenches (e.g., formed in suitable electrode materials, or as a result of stacking layers of electrochemical single-cell batteries, rolling up multilayer electrochemical single-cell batteries, etc.), as will be understood by those skilled in the art upon reading this disclosure.

[0153] Optionally, the electrode may be coated with a protective layer designed to promote or mitigate predetermined chemical or physical interactions with other components of the electrochemical cell, such as reactions that consume electrode active materials, the formation of dendritic structures extending from the electrode, etc., as will be understood by one of ordinary skill in the art upon reading this disclosure. Similarly, the electrode may comprise a plurality of particles (e.g., particles of active material) dispersed within or throughout a binder (e.g., a polymer matrix), and the binder may be or comprise materials that promote or mitigate desired or undesired interactions within the electrochemical cell. In further embodiments, the electrolyte may be operatively, chemically, or electrically coupled to a membrane or multiple membranes configured (e.g., based on physical properties such as porosity, non-porosity, spatial arrangement, surface area, etc., or chemical configuration, such as based on chemical composition, specific functionalization (e.g., functionalization of the membrane surface), etc.) to isolate the electrolyte and / or chemicals formed or derived therefrom from other components of the electrochemical cell.

[0154] In a particularly preferred method, the electrode may comprise one or more carbonaceous materials, such as Figure 12 As shown and described in more detail below.

[0155] It will be understood that the electrolyte according to the presently disclosed inventive concept may have any suitable chemical composition that a person skilled in the art would understand when considering the specific context of an electrochemical single cell (e.g., the chemical composition and structural arrangement of various other components included in an electrochemical single cell).

[0156] Similarly, electrolytes present in various electrochemical single-cell batteries can be in liquid form, can be or include solid electrolyte compositions, can be or include gel phases or gel-based electrolytes (such as gel polymer electrolytes), or any combination thereof that would be apparent to those skilled in the art upon reading this disclosure. Likewise, electrolytes can include semi-solid compositions, such as gels, slurries, suspensions, etc., as would be apparent to those skilled in the art upon reading this disclosure.

[0157] The separator, which may be omitted according to certain aspects of the inventive concept described herein, may be or include any suitable composition or structure known in the art and that will be conceived by one of ordinary skill in reading this disclosure as compatible with the composition and / or structure of the invention described herein. For example, the separator may include an impermeable solid structure, a semi-permeable membrane, or a selectively permeable composition (i.e., according to various embodiments, a composition permeable to one or more predetermined chemical substances but impermeable or substantially impermeable to selected or all of the other chemical substances). For example, the separator may be configured to functionally separate or isolate different components of an electrochemical single-cell battery from each other physically, chemically, electrically, or otherwise, in order to avoid undesirable chemical reactions (such as parasitic reactions between the electrolyte or its derivatives and the electrodes, polysulfide shuttle, dendrite formation, etc., as will be understood by one of ordinary skill in the art upon reading this specification).

[0158] Furthermore, any exemplary electrochemical cell with a construction described herein or an equivalent construction that would occur to a person skilled in the art upon reading this disclosure may include one or more mechanisms for mitigating or preventing parasitic reactions between the electrode and the electrolyte (and substances formed or derived from the electrode or electrolyte during operation of the electrochemical cell) or other chemicals present in the electrochemical cell environment. These mechanisms may be inherent to one or more of the exemplary structures described above (e.g., electrodes, separators, electrolytes, etc.) or may be specifically configured via specific modifications, functionalizations, structural arrangements, etc., of specific components of the electrochemical cell. Any such characteristics, whether inherent or specifically configured, are described in more detail herein according to various exemplary embodiments of the inventive concept now disclosed.

[0159] From the foregoing general description and the corresponding figures, those skilled in the art will realize that, according to different embodiments, the electrochemical cell described herein includes various components, each playing a specific core role in the overall function of the electrochemical cell (e.g., electrodes facilitate electrical contact between the electrolyte and the external environment of the electrochemical cell; separators separate or isolate various components, chemicals, etc., within the electrochemical cell environment; and the electrolyte facilitates charge transfer between the electrodes of the electrochemical cell). These components may optionally perform or transmit one or more additional functions for the electrochemical cell. For example, and as mentioned above, electrodes or separators, in addition to their respective core functions, may also act as current collectors, thereby allowing the omission of a separate (typically heavy metal) structure dedicated to collecting the current generated by the electrochemical cell.

[0160] In all respects, any one or more components of the electrochemical single-cell battery arrangement described herein may include one or more carbonaceous materials, including but not limited to... Figure 12 Those shown. For example, some components may include carbonaceous materials, in addition to those mentioned above. Figure 8A-11 In addition to the various components shown and described, carbonaceous materials may also be included, or both, as those skilled in the art will understand upon reading this disclosure. In numerous embodiments, exemplary carbonaceous materials may include, but are not limited to, carbon black, carbon nanotubes (CNO), necked CNO, carbon nanospheres, graphite, pyrolytic graphite, graphene, graphene nanoparticles, graphene sheets, three-dimensional (3D) graphene, graphene oxide, fullerene, hybrid fullerene, single-walled nanotubes, multi-walled nanotubes, carbon dots, carbon spheres, porous carbon, carbon fibers, etc., as those skilled in the art will understand upon reading this specification. (Li et al., in “Synthesis, modification strategies and applications of coal-based materials”,...) Fuel Processing Tech. Further details regarding the preparation and properties of selected carbonaceous materials are provided in , 230:1, 107203 (June 2022) (https: / / doi.org / 10.1016 / j.fuproc.2022.107203), particularly Figure 12 Those shown in the image.

[0161] Furthermore, according to various embodiments, particularly the exemplary components of the electrochemical single cell described above as shown in Figures 8-11, can exist in a single cell “stack” (e.g., two opposing electrodes with corresponding separators, electrolytes, etc. arranged between them) or in a repeating (e.g., layered) structure. A simplified repeating structure may, for example, include a first cathode (optionally coupled to a first cathode current collector) at one end of the electrochemical single cell, adjacent to a first electrolyte, which in turn is adjacent to a first separator, which in turn is adjacent to a second electrolyte, which in turn is adjacent to a first anode (optionally coupled to a first anode current collector) disposed opposite the first cathode of the electrochemical single cell, together forming a single electrochemical single cell layer. The repeating structure may further include additional electrolytes, separators, and electrode structures in a similar manner to form a multilayer repeating pattern within the resulting electrochemical single cell.

[0162] Regardless of whether repeating structures are included, various methods allow for the manipulation, configuration, and arrangement of electrochemical single-cell batteries during the fabrication of larger structures (such as batteries). For example, and as those skilled in the art will recognize upon reading the inventive concept described herein, in some methods, according to one embodiment, such as Figure 8B The electrochemical single cell shown can be "wound" around a central axis to form a so-called "jelly roll" structure, such as... Figure 8CAs shown, it may be particularly suitable for certain arrangements or applications, such as for cylindrical or prismatic electrochemical single-cell batteries, as will be understood by those skilled in the art upon reading this disclosure.

[0163] While the aforementioned electrode, electrolyte, and separator components are the most common and critical aspects of the exemplary electrochemical single-cell batteries described herein, it will be understood that, according to various embodiments, the electrochemical single-cell battery may or may not include any suitable combination or arrangement of additional or alternative components, such as membranes, housings, caps, shells, wrappers, springs, wires, spacers, lugs, contacts, leads, gaskets, compression structures, or mechanisms, as will be understood by one of ordinary skill in the art upon reading this specification.

[0164] Furthermore, it will be understood that, without departing from the scope of the inventive concept of this disclosure, those skilled in the art can employ the various electrochemical single-cell battery embodiments described herein in any effective arrangement or combination, including but not limited to coin cell arrangements, cylindrical cell arrangements, pouch cell arrangements, prismatic cell arrangements, etc., or any suitable equivalent arrangements that those skilled in the art will understand upon reading this disclosure. For example, multiple identical arrangements, combinations of different arrangements, or both may be employed, for example, to form a battery or component (e.g., a battery module or battery pack, as will be understood by those skilled in the art upon reading this disclosure).

[0165] For example, those skilled in the art will appreciate that the different arrangements described herein may have different advantages or disadvantages in different application contexts, and that the arrangement most advantageous for the particular application of interest may be selected. Alternatively, those skilled in the art may include different arrangements to provide robustness to the resulting structure across different applications or operating conditions, provide flexibility of use, redundancy of points of failure, or other advantages that those skilled in the art will understand based on the specific application considered.

[0166] As a specific example, cylindrical single-cell batteries are more prone to cracking compared to other arrangements described herein. Therefore, such as Figure 10A and 10B The cylindrical cell arrangement shown may not be suitable for, for example, Figure 11The prismatic cell configurations shown are compatible with or depend on the intended application of the given electrochemical cell, such as applications involving significant and / or frequent application of mechanical forces (e.g., rapid acceleration / deceleration, vibration, etc., as often experienced in vehicle applications). Similarly, pouch cell arrangements are particularly sensitive to volume expansion and contraction that occur during normal operation and cycling of the electrochemical cell and may require or benefit from additional support, such as compression structures or internal mechanisms (e.g., polymeric support networks as described in U.S. Patent No. 12,009,531, entitled “Internally enclosed support system for batteries, fabrication techniques and applications for the same,” granted June 11, 2024, the contents of which are incorporated herein by reference).

[0167] Furthermore, while the exemplary electrochemical cell arrangements clearly described herein and shown in the various figures include pouch cell arrangements, coin cell arrangements, cylindrical cell arrangements, and prismatic cell arrangements, other arrangements and / or components may be utilized without departing from the scope of the inventive concept set forth in this disclosure. For example, electrochemical cell arrangements may additionally or alternatively include components or be characterized by arrangements such as chassis, trays, bags, modules, components, housings, etc., as will be understood by one of ordinary skill in the art upon reading this disclosure.

[0168] Of course, according to various embodiments, the electrochemical cell described herein may include external components at least partially surrounding the electrochemical cell. For example, exemplary external components may be selected from a housing surrounding the electrochemical cell, a module operatively coupled to the electrochemical cell, an assembly operatively coupled to the electrochemical cell, a pack surrounding the electrochemical cell, a bag surrounding the electrochemical cell, a casing surrounding the electrochemical cell, a tray operatively coupled to the electrochemical cell, a disc operatively coupled to the electrochemical cell, and combinations thereof. The assembly may include: a parallel assembly, a series assembly, or a cell-chassis assembly. In a further embodiment, the electrochemical cell may be integrated into or be part of a structural component of a device that supplies power to the electrochemical cell, such as integration into a structural component of an electric vehicle.

[0169] The inventive concepts described herein include the use of additive manufacturing technology, injection molding technology, compression molding technology, hybrid injection / compression molding technology, preforming technology, hand lay-up molding technology, casting technology, infusion technology, sintering technology, or any combination thereof that a person skilled in the art would conceive of upon reading this disclosure to fabricate various types of electrochemical single-cell batteries.

[0170] It should be understood that the arrangement of components shown in the accompanying drawings is exemplary, and other arrangements are possible. It should also be understood that the various system components (and devices) defined by the claims below and shown in the various block diagrams represent logical components in some systems configured according to the subject matter disclosed herein.

[0171] For example, one or more of these system components (and devices) can be implemented wholly or partially by at least some of the components shown in the arrangement illustrated in the figures. Furthermore, while at least one of these components is implemented at least partially as an electronic hardware component and thus constitutes a machine, other components can be implemented in software, which, when included in an execution environment, constitutes a machine, hardware, or a combination of software and hardware.

[0172] More specifically, at least one component as defined in the claims is at least partially implemented as an electronic hardware component, such as an instruction execution machine (e.g., a processor-based or processor-containing machine) and / or a dedicated circuit or circuit system (e.g., discrete logic gates interconnected to perform a specific function). Other components may be implemented in software, hardware, or a combination of software and hardware. Furthermore, some or all of these other components may be combined, some may be omitted entirely, and additional components may be added while still achieving the functionality described herein. Therefore, the subject matter described herein can be implemented in many different variations, and all such variations are covered within the scope of the claims.

[0173] In the foregoing description, unless otherwise indicated, the subject matter is described with reference to the actions and symbolic representations of operations performed by one or more devices. Therefore, it will be understood that such actions and operations, sometimes referred to as those performed by a computer, involve the manipulation of data in a structured form by a processor. This manipulation transforms the data or stores it in a location within the computer's memory system, thereby reconfiguring or otherwise altering the operation of the device in a manner fully understood by those skilled in the art. The data is stored in a physical location in memory as a data structure having specific properties defined by the data format. However, while the subject matter has been described in the foregoing context, this is not intended to be limiting, as those skilled in the art will appreciate that the various actions and operations described below can also be implemented in hardware.

[0174] To facilitate understanding of the subject matter described herein, many aspects are described in order of action. At least one of these aspects, as defined by the claims, is performed by electronic hardware components. For example, it will be appreciated that various actions may be performed by a dedicated circuit or circuit system, program instructions executed by one or more processors, or a combination of both. The description of any order of actions herein is not intended to imply that a particular order of execution described herein must be followed. Unless otherwise indicated herein or otherwise obviously contradicted by the context, all methods described herein may be performed in any suitable order.

[0175] Unless otherwise indicated herein or otherwise obviously contradictory in the context, the use of the terms “an” and “the”, and similar designations, in the context of describing the subject matter (particularly in the context of the following claims) should be interpreted as encompassing both the singular and plural. Unless otherwise indicated herein, the description of numerical ranges herein is intended only as a shorthand for each individual value falling within that range, and each individual value is incorporated into the specification as if it were described separately herein. Furthermore, the foregoing description is for illustrative purposes only and not for limiting purposes, as the scope of protection sought is defined by the claims given below and any valid equivalents thereof. The use of any and all instances or exemplary language provided herein (e.g., “such as”) is intended only to better illustrate the subject matter and does not constitute a limitation on the scope of the subject matter unless otherwise claimed. The use of the term “based on” and other similar phrases indicating conditions leading to the result in the claims and the textual description is not intended to exclude any other conditions leading to that result. No language in the specification should be construed as indicating that any unclaimed element is necessary for practicing the claimed invention.

[0176] The embodiments described herein include one or more modes known to the inventors for implementing the claimed subject matter. Of course, variations of these embodiments will become apparent to those skilled in the art after reading the foregoing specification. The inventors anticipate that those skilled in the art will appropriately employ such variations, and the inventors intend to practice the claimed subject matter in ways different from those specifically described herein. Therefore, the claimed subject matter includes all modifications and equivalents of the subject matter recited in the appended claims as permitted by applicable law. Furthermore, unless otherwise indicated herein or otherwise obviously contradicted by the context, any combination of the foregoing elements in all possible variations is covered.

[0177] For example, according to one embodiment, the inventive concept presented herein includes any suitable combination or arrangement of one or more of the following compounds, features, structures, etc., which will be understood by one of ordinary skill in the art upon reading this disclosure: an electrolyte system comprising: at least one solvent; at least one electron-withdrawing compound; at least one performance-enhancing additive; and at least one lithium-ion transport compound. The at least one solvent may include at least one ether, and is preferably selected from: dimethoxyethane (DME), dioxolane (DOL), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), toluene, tetramethylurea (TMU), tetrabutylammonium hydroxide (TBA), dimethylacetamide (DMA), tetrahydrofuran (THF), diethylene glycol dimethyl ether (diethylene glycol dimethyl ether or DEGDME), acetonitrile (ACN), dimethyl trisulfide (DMTS), diisopropyl ether (DIPE), tetrahydrofuran (THF), 1,2-diamine Dimethyl propane (DAP), triethylene glycol dimethyl ether (trigDME), tetraethylene glycol dimethyl ether (TEGDME), sulfolane (SUL), methyl tert-butyl ether (MTBE), 2,2,3,3-tetrafluoro-1,4-dimethoxybutane (FDMB), bis(2,2,2,trifluoroethyl) ether (BTFE), 1H,1H,5H-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether (OFE), (1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE) 2,2,2-Trifluoroethyl 1,1,2,2-Tetrafluoroethyl ether (TFETFE), 1,1,2,2-Tetrafluoroethyl isobutyl ether (TFEIE), 1,1,2,3,3,3-Hexafluoropropyl 2,2,2-Trifluoroethyl ether (THE), Methoxyperfluorobutane (MPB), Bis(2,2-difluoroethyl) ether (DFE), 2,2,2-Trifluoroethyl methyl ether (TFEME), Bis(2-fluoroethyl) ether (BFE), Bis(2,2,2,trifluoroethyl) ether (BTFE), 3-Fluoropyridine (3FP), 1 The solvent comprises 2-(1,1,2,2-tetrafluoroethoxy)ethane (TFEE), 1,2-dimethoxy-1,1,2,2-tetrafluoroethane (DMETF), 2-methyl-1-(1,1,2,2-tetrafluoroethoxy)propane (TFEIBE), bis(2,2,3,3,3-pentafluoropropyl) ether (BPFPE), allyl 2,2,3,3,3-pentafluoropropyl ether (APFPE), hydrocarbons, and combinations thereof. The at least one solvent is present in an aggregate amount ranging from greater than 0 vol% of the electrolyte system to about 75 vol% of the electrolyte system.Furthermore, at least one electron-withdrawing group comprises at least one compound characterized by an α-hydrogenated β-functionalized unit, and preferably includes at least one electron-withdrawing compound selected from: 2,2-dimethoxy-4-trifluoromethyl-1,3-dioxolane (DTDL), 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG), 1,1,1,14,14,14-hexafluoro-3,6,9,12-tetraoxatetradecane (FTrG), 1,1,1,17,17,17-hexafluoro-3,6,9,12,15-pentaheptadecane (FTeG), bis(2,2-difluoroethyl) ether (BDE), bis(2,2, 2,2,2-Trifluoroethyl ether (BTFE), 2,2,2-trifluoroethyl-2-fluoroethyl ether (TFFE), 1,1-difluoroethyl-2-fluoroethyl ether (DFE), fluorinated 1,4-dimethoxybutane (FDMB), 3-fluoropyridine (3FP), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,3,3-tetrafluoropropyl) ether (BTFPE), 2,2,2-trifluoroethyl-1,1,2,2-tetrafluoroethyl ether (TFTFE), tris(2,2,2-trifluoroethyl) phosphate, bis(2,2,2-trifluoroethyl) methylphosphonate, isosorbide dinitrate (ISDN), bis(2-fluoroethyl) ether (BFE), and combinations thereof. The at least one electron-withdrawing compound is preferably present in an accumulated amount ranging from greater than 0 vol% to about 75 vol% of the electrolyte system. The at least one performance-enhancing additive contains dicyandiamide (DCDA) at about 0.01%. M To approximately 0.2 M The lithium-ion transport compound is present in amounts within the specified range. The at least one lithium-ion transport compound comprises at least one lithium salt, and is preferably selected from: lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO3), lithium perchlorate (LiClO4), lithium difluoro(oxaloyl)borate (LiFOB), lithium bis(oxaloyl)borate (LiBOB), lithium trifluoromethanesulfonate (LiTf), lithium bis(pentafluoroethanesulfonyl)imide (LiBETi), lithium bis(fluorosulfonyl)imide (LiFSI), lithium trifluoroacetate (LiTFAc), and combinations thereof. The lithium-ion transport compound is present in amounts of approximately 0.1... M To about 10 MThe electrolyte system may contain at least one chalcogenide, preferably selected from dimethyl diselenyl ether (DMDSe), diphenyl diselenyl ether (DPDSe), dimethyl ditelluride (DMDTe), diphenyl ditelluride (DPDTe), and combinations thereof, and preferably in an amount ranging from about 0.1% by weight to about 3.0% by weight. The electrolyte system of the present invention can be implemented in electrochemical single-cell batteries having the structures described herein, including pouch structures, coin structures, cylindrical structures, or prismatic structures. The electrochemical single-cell batteries may or may not include different structures used as current collectors.

[0178] According to another embodiment, the inventive concept presented herein includes any suitable combination or arrangement of one or more of the following compounds, features, structures, etc., which will be understood by those skilled in the art upon reading this disclosure: an electrolyte system comprising: a solvent system; at least one electron-withdrawing compound; and at least one lithium-ion transport compound. The solvent system comprises at least one solvent, preferably selected from: dimethoxyethane (DME), dioxolane (DOL), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), toluene, tetramethylurea (TMU), tetrabutylammonium hydroxide (TBA), dimethylacetamide (DMA), tetrahydrofuran (THF), diethylene glycol dimethyl ether (diethylene glycol dimethyl ether or DEGDME), acetonitrile (ACN), dimethyl trisulfide (DMTS), diisopropyl ether (DIPE), tetrahydrofuran (THF), 1,2-di... Aminopropane (DAP), triethylene glycol dimethyl ether (trigDME), tetraethylene glycol dimethyl ether (TEGDME), sulfolane (SUL), methyl tert-butyl ether (MTBE), 2,2,3,3-tetrafluoro-1,4-dimethoxybutane (FDMB), bis(2,2,2,trifluoroethyl) ether (BTFE), 1H,1H,5H-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether (OFE), (1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether ( TTE), 2,2,2-trifluoroethyl 1,1,2,2-tetrafluoroethyl ether (TFETFE), 1,1,2,2-tetrafluoroethyl isobutyl ether (TFEIE), 1,1,2,3,3,3-hexafluoropropyl 2,2,2-trifluoroethyl ether (THE), perfluoromethoxybutane (MPB), bis(2,2-difluoroethyl) ether (DFE), 2,2,2-trifluoroethyl methyl ether (TFEME), bis(2-fluoroethyl) ether (BFE), bis(2,2,2,trifluoroethyl) ether (BTFE), 3-fluoropyridine (3FP), 1,2-(1,1,2,2-tetrafluoroethoxy)ethane (TFEE), 1,2-dimethoxy-1,1,2,2-tetrafluoroethane (DMETF), 2-methyl-1-(1,1,2,2-tetrafluoroethoxy)propane (TFEIBE), bis(2,2,3,3,3-pentafluoropropyl) ether (BPFPE), allyl 2,2,3,3,3-pentafluoropropyl ether (APFPE), hydrocarbons and combinations thereof. The solvent system comprises more than 0% by volume of the electrolyte system to approximately 75% by volume of the electrolyte system.Furthermore, at least one electron-withdrawing group comprises at least one compound characterized by an α-hydrogenated β-functionalized unit, and preferably includes at least one electron-withdrawing compound selected from: 2,2-dimethoxy-4-trifluoromethyl-1,3-dioxolane (DTDL), 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG), 1,1,1,14,14,14-hexafluoro-3,6,9,12-tetraoxatetradecane (FTrG), 1,1,1,17,17,17-hexafluoro-3,6,9,12,15-pentaheptadecane (FTeG), bis(2,2-difluoroethyl) ether (BDE), bis(2,2, 2,2,2-Trifluoroethyl ether (BTFE), 2,2,2-trifluoroethyl-2-fluoroethyl ether (TFFE), 1,1-difluoroethyl-2-fluoroethyl ether (DFE), fluorinated 1,4-dimethoxybutane (FDMB), 3-fluoropyridine (3FP), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,3,3-tetrafluoropropyl) ether (BTFPE), 2,2,2-trifluoroethyl-1,1,2,2-tetrafluoroethyl ether (TFTFE), tris(2,2,2-trifluoroethyl) phosphate, bis(2,2,2-trifluoroethyl) methylphosphonate, isosorbide dinitrate (ISDN), bis(2-fluoroethyl) ether (BFE), and combinations thereof. The at least one electron-withdrawing compound is preferably present in an accumulated amount ranging from greater than 0 vol% to about 75 vol% of the electrolyte system. The at least one electron-withdrawing compound comprises at least one α-hydrogenated selective β-modified moiety, and the at least one α-hydrogenated selective β-modified moiety does not contain fluorine. In other respects, the at least one electron-withdrawing compound does not contain fluorine. The at least one lithium-ion transport compound comprises at least one lithium salt, and is preferably selected from: lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO3), lithium perchlorate (LiClO4), lithium difluoro(oxaloyl)borate (LiFOB), lithium bis(oxaloyl)borate (LiBOB), lithium trifluoromethanesulfonate (LiTf), lithium bis(pentafluoroethanesulfonyl)imide (LiBETi), lithium bis(fluorosulfonyl)imide (LiFSI), lithium trifluoroacetate (LiTFAc), and combinations thereof. The at least one lithium-ion transport compound is present at about 0.1... M To about 10 M The amount present is within the range. The electrolyte system of the present invention can be implemented in electrochemical single-cell batteries having the construction described herein, including pouch construction, coin construction, cylindrical construction, or prismatic construction. The electrochemical single-cell battery may or may not include different structures used as current collectors.

[0179] In further embodiments, the lithium-based anode includes any suitable combination or arrangement of one or more of the following compounds, features, structures, etc., which will be understood by one of ordinary skill in the art upon reading this disclosure: an interfacial phase formed on the surface of the lithium-based anode, wherein the interfacial phase is formed by the interaction between the active material of the lithium-based anode and a derivative of at least one electron-withdrawing compound. The at least one electron-withdrawing compound preferably comprises at least one α-hydrogenated selective β-modified moiety, wherein the at least one α-hydrogenated selective β-modified moiety does not contain fluorine, and / or the at least one electron-withdrawing compound is entirely free of fluorine. Preferably, the at least one electron-withdrawing compound comprises at least one electron-withdrawing compound selected from: 2,2-dimethoxy-4-trifluoromethyl-1,3-dioxolane (DTDL), 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG), 1,1,1,14,14,14-hexafluoro-3,6,9,12-tetraoxatetradecane (FTrG), 1,1,1,17,17,17-hexafluoro-3,6,9,12,15-pentaheptadecane (FTeG), bis(2,2-difluoroethyl) ether (BDE), bis(2,2,2,trifluoroethyl) ether (BTFE) The active material of the lithium-based anode preferably comprises elemental lithium or a lithium alloy, wherein the lithium alloy comprises lithium-magnesium, lithium-sulfur, or a combination thereof. The anode of this invention can be implemented in an electrochemical single-cell battery having the construction described herein, including pouch construction, coin construction, cylindrical construction, or prismatic construction. The electrochemical single-cell battery may or may not include different structures used as current collectors.

[0180] In further embodiments, the electrolyte system comprises any suitable combination or arrangement of one or more of the following compounds, features, structures, etc., which will be understood by those skilled in the art upon reading this disclosure: a solvent system; at least one electron-withdrawing compound; at least one lithium-ion transport compound; and at least one chalcogenide. The solvent system comprises at least one solvent, preferably selected from: dimethoxyethane (DME), dioxolane (DOL), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), toluene, tetramethylurea (TMU), tetrabutylammonium hydroxide (TBA), dimethylacetamide (DMA), tetrahydrofuran (THF), diethylene glycol dimethyl ether (diethylene glycol dimethyl ether or DEGDME), acetonitrile (ACN), dimethyl trisulfide (DMTS), diisopropyl ether (DIPE), tetrahydrofuran (THF), 1,2-di(di(ethylene glycol dimethyl ether or DEGDME) ... Aminopropane (DAP), triethylene glycol dimethyl ether (trigDME), tetraethylene glycol dimethyl ether (TEGDME), sulfolane (SUL), methyl tert-butyl ether (MTBE), 2,2,3,3-tetrafluoro-1,4-dimethoxybutane (FDMB), bis(2,2,2,trifluoroethyl) ether (BTFE), 1H,1H,5H-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether (OFE), (1,1,2,2-tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether ( TTE), 2,2,2-trifluoroethyl 1,1,2,2-tetrafluoroethyl ether (TFETFE), 1,1,2,2-tetrafluoroethyl isobutyl ether (TFEIE), 1,1,2,3,3,3-hexafluoropropyl 2,2,2-trifluoroethyl ether (THE), perfluoromethoxybutane (MPB), bis(2,2-difluoroethyl) ether (DFE), 2,2,2-trifluoroethyl methyl ether (TFEME), bis(2-fluoroethyl) ether (BFE), bis(2,2,2,trifluoroethyl) ether (BTFE), 3-fluoropyridine (3FP), 1,2-(1,1,2,2-tetrafluoroethoxy)ethane (TFEE), 1,2-dimethoxy-1,1,2,2-tetrafluoroethane (DMETF), 2-methyl-1-(1,1,2,2-tetrafluoroethoxy)propane (TFEIBE), bis(2,2,3,3,3-pentafluoropropyl) ether (BPFPE), allyl 2,2,3,3,3-pentafluoropropyl ether (APFPE), hydrocarbons and combinations thereof. The solvent system comprises more than 0% by volume of the electrolyte system to approximately 75% by volume of the electrolyte system.Furthermore, at least one electron-withdrawing group comprises at least one compound characterized by an α-hydrogenated β-functionalized unit, and preferably includes at least one electron-withdrawing compound selected from: 2,2-dimethoxy-4-trifluoromethyl-1,3-dioxolane (DTDL), 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG), 1,1,1,14,14,14-hexafluoro-3,6,9,12-tetraoxatetradecane (FTrG), 1,1,1,17,17,17-hexafluoro-3,6,9,12,15-pentaheptadecane (FTeG), bis(2,2-difluoroethyl) ether (BDE), bis(2,2, 2,2,2-Trifluoroethyl ether (BTFE), 2,2,2-trifluoroethyl-2-fluoroethyl ether (TFFE), 1,1-difluoroethyl-2-fluoroethyl ether (DFE), fluorinated 1,4-dimethoxybutane (FDMB), 3-fluoropyridine (3FP), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,3,3-tetrafluoropropyl) ether (BTFPE), 2,2,2-trifluoroethyl-1,1,2,2-tetrafluoroethyl ether (TFTFE), tris(2,2,2-trifluoroethyl) phosphate, bis(2,2,2-trifluoroethyl) methylphosphonate, isosorbide dinitrate (ISDN), bis(2-fluoroethyl) ether (BFE), and combinations thereof. The at least one electron-withdrawing compound is preferably present in an accumulated amount ranging from greater than 0 vol% to about 75 vol% of the electrolyte system. The at least one electron-withdrawing compound comprises at least one α-hydrogenated selective β-modified moiety, and the at least one α-hydrogenated selective β-modified moiety does not contain fluorine. In other aspects, the at least one electron-withdrawing compound does not contain fluorine. The at least one lithium-ion transport compound comprises at least one lithium salt, and is preferably selected from: lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO3), lithium perchlorate (LiClO4), lithium difluoro(oxaloyl)borate (LiFOB), lithium bis(oxaloyl)borate (LiBOB), lithium trifluoromethanesulfonate (LiTf), lithium bis(pentafluoroethanesulfonyl)imide (LiBETi), lithium bis(fluorosulfonyl)imide (LiFSI), lithium trifluoroacetate (LiTFAc), and combinations thereof. The lithium-ion transport compound is present in approximately 0.1... M To about 10 MThe presence of the at least one chalcogenide is selected from: dimethyl diselenyl ether (DMDSe), diphenyl diselenyl ether (DPDSe), dimethyl ditelluride ether (DMDTe), diphenyl ditelluride ether (DPDTe), and combinations thereof, and preferably in an amount ranging from about 0.1% by weight to about 3.0% by weight. The electrolyte system of the present invention can be implemented in electrochemical single-cell batteries having the construction described herein, including pouch construction, coin construction, cylindrical construction, or prismatic construction. The electrochemical single-cell battery may or may not include different structures used as current collectors.

Claims

1. An electrolyte system comprising: At least one solvent; At least one electron-withdrawing compound; At least one performance-enhancing additive; and At least one lithium-ion transport compound.

2. The electrolyte system of claim 1, wherein the at least one solvent comprises at least one ether.

3. The electrolyte system of claim 1, wherein the at least one solvent is selected from: dimethoxyethane (DME), dioxolane (DOL), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), toluene, tetramethylurea (TMU), tetrabutylammonium hydroxide (TBA), dimethylacetamide (DMA), tetrahydrofuran (THF), diethylene glycol dimethyl ether (diethylene glycol dimethyl ether or DEGDME), acetonitrile (ACN), dimethyl trisulfide (DMTS), diisopropyl ether (DIPE), tetramethyl ether, dimethyl sulfide (DMS), dimethyl sulfide (DIPE), ...DIPE), dimethyl sulfide (DIPE), dimethyl sulfide (DIPE), dimethyl sulfide (DIPE), dimethyl sulfide (DIPE), dimethyl sulfide (DIPE), dimethyl sulfide (DIPE), dimethyl sulfide (DIPE), dimethyl sulfide (DIPE), dimethyl sulfide (DIPE), dimethyl sulfide (DIPE), dimethyl sulfide (DIPE), dimethyl sulfide (DIPE), dimethyl sulfide (DIPE), dimethyl sulfide (DIPE), dimethyl sulfide (DIPE), dimethyl sulfide Hydrogen furan (THF), 1,2-diaminopropane (DAP), triethylene glycol dimethyl ether (trigDME), tetraethylene glycol dimethyl ether (TEGDME), sulfolane (SUL), methyl tert-butyl ether (MTBE), 2,2,3,3-tetrafluoro-1,4-dimethoxybutane (FDMB), bis(2,2,2,trifluoroethyl) ether (BTFE), 1H,1H,5H-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether (OFE), (1,1,2, 2-Tetrafluoroethyl 2,2,3,3-tetrafluoropropyl ether (TTE), 2,2,2-trifluoroethyl 1,1,2,2-tetrafluoroethyl ether (TFETFE), 1,1,2,2-tetrafluoroethyl isobutyl ether (TFEIE), 1,1,2,3,3,3-hexafluoropropyl 2,2,2-trifluoroethyl ether (THE), perfluoromethoxybutane (MPB), bis(2,2-difluoroethyl) ether (DFE), 2,2,2-trifluoroethyl methyl ether (TFEME), bis(2-fluoroethyl) ether (BFE) Bis(2,2,2,trifluoroethyl) ether (BTFE), 3-fluoropyridine (3FP), 1,2-(1,1,2,2-tetrafluoroethoxy)ethane (TFEE), 1,2-dimethoxy-1,1,2,2-tetrafluoroethane (DMETF), 2-methyl-1(1,1,2,2-tetrafluoroethoxy)propane (TFEIBE), bis(2,2,3,3,3-pentafluoropropyl) ether (BPFPE), allyl 2,2,3,3,3-pentafluoropropyl ether (APFPE), hydrocarbons and combinations thereof.

4. The electrolyte system of claim 1, wherein the at least one solvent is present in a cumulative amount ranging from more than 0% by volume to about 75% by volume of the electrolyte system.

5. The electrolyte system of claim 1, wherein at least one electron-withdrawing group comprises at least one compound characterized by an α-hydrogenated β-functionalized unit.

6. The electrolyte system of claim 1, wherein the at least one electron-withdrawing compound is selected from: 2,2-dimethoxy-4-trifluoromethyl-1,3-dioxolane (DTDL), 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG), 1,1,1,14,14,14-hexafluoro-3,6,9,12-tetraoxatetradecane (FTrG), 1,1,1,17,17,17-hexafluoro-3,6,9,12,15-pentaheptadecane (FTeG), bis(2,2-difluoroethyl) ether (BDE), bis(2,2,2,trifluoroethyl) ether (BTFE) ), 2,2,2-trifluoroethyl-2-fluoroethyl ether (TFFE), 1,1-difluoroethyl-2-fluoroethyl ether (DFE), fluorinated 1,4-dimethoxybutane (FDMB), 3-fluoropyridine (3FP), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,3,3-tetrafluoropropyl) ether (BTFPE), 2,2,2-trifluoroethyl-1,1,2,2-tetrafluoroethyl ether (TFTFE), tris(2,2,2-trifluoroethyl) phosphate, bis(2,2,2-trifluoroethyl) methylphosphonate, isosorbide dinitrate (ISDN), bis(2-fluoroethyl) ether (BFE), and combinations thereof.

7. The electrolyte system of claim 1, wherein the at least one electron-withdrawing compound is present in an accumulated amount ranging from more than 0% by volume to about 75% by volume of the electrolyte system.

8. The electrolyte system of claim 1, wherein the at least one performance-enhancing additive is selected from: acetonitrile, azobisisobutyronitrile (AIBN), cyanamide, lithium dicyandiamide, dicyandiamide (DCDA), guanine, guanidine nitrate, guanidine thiocyanate, guanidine p-toluenesulfonate, guanidine trifluoromethanol, 2-guanidinobenzimidazole, guanidine hydrochloride, guanidine carbonate, guanidine bromide, guanidine iodide, guanidine acetate, guanidine sulfate, guanidine phosphate, succinate, or any combination thereof.

9. The electrolyte system of claim 1, wherein the at least one performance-enhancing additive is present in an amount ranging from about 0.01 M to about 0.2 M.

10. The electrolyte system of claim 1, wherein the at least one lithium-ion transport compound comprises at least one lithium salt.

11. The electrolyte system of claim 1, wherein the at least one lithium-ion transport compound is selected from: lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO3), lithium perchlorate (LiClO4), lithium difluoro(oxaloyl)borate (LiFOB), lithium bis(oxaloyl)borate (LiBOB), lithium trifluoromethanesulfonate (LiTf), lithium bis(pentafluoroethanesulfonyl)imide (LiBETi), lithium bis(fluorosulfonyl)imide (LiFSI), lithium trifluoroacetate (LiTFAc), and combinations thereof.

12. The electrolyte system of claim 1, wherein the at least one lithium-ion transport compound is present in an amount ranging from about 0.1 M to about 10 M.

13. The electrolyte system of claim 1, wherein it comprises at least one chalcogenide.

14. The electrolyte system of claim 13, wherein the at least one chalcogenide is selected from: dimethyl diselenyl ether (DMDSe), diphenyl diselenyl ether (DPDSe), dimethyl ditelluride (DMDTe), diphenyl ditelluride (DPDTe), and combinations thereof.

15. The electrolyte system of claim 13, wherein the at least one chalcogenide is present in a cumulative amount ranging from about 0.1% by weight to about 3.0% by weight.

16. An electrochemical single-cell battery comprising the electrolyte system as described in claim 1.

17. The electrochemical single cell of claim 16, wherein the electrochemical single cell is characterized by a pouch structure.

18. The electrochemical single cell of claim 16, wherein the electrochemical single cell is characterized by a coin-like structure.

19. The electrochemical single cell of claim 16, wherein the electrochemical single cell is characterized by a cylindrical structure.

20. The electrochemical single cell of claim 16, wherein the electrochemical single cell is characterized by a prismatic structure.

21. An electrolyte system comprising: Solvent system; At least one electron-withdrawing compound; At least one lithium-ion transport compound; and At least one chalcogenide.

22. The electrolyte system of claim 21, wherein the solvent system comprises at least one solvent selected from the group consisting of: dimethoxyethane (DME), dioxolane (DOL), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), toluene, tetramethylurea (TMU), tetrabutylammonium hydroxide (TBA), dimethylacetamide (DMA), tetrahydrofuran (THF), diethylene glycol dimethyl ether (diethylene glycol dimethyl ether or DEGDME), acetonitrile (ACN), dimethyl trisulfide (DMTS), and diisopropyl ether. (DIPE), tetrahydrofuran (THF), 1,2-diaminopropane (DAP), triethylene glycol dimethyl ether (trigDME), tetraethylene glycol dimethyl ether (TEGDME), sulfolane (SUL), methyl tert-butyl ether (MTBE), 2,2,3,3-tetrafluoro-1,4-dimethoxybutane (FDMB), bis(2,2,2,trifluoroethyl) ether (BTFE), 1H,1H,5H-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether (OFE), ( 1,1,2,2-Tetrafluoroethyl 2,2,3,3-Tetrafluoropropyl ether (TTE), 2,2,2-Trifluoroethyl 1,1,2,2-Tetrafluoroethyl ether (TFETFE), 1,1,2,2-Tetrafluoroethyl isobutyl ether (TFEIE), 1,1,2,3,3,3-Hexafluoropropyl 2,2,2-Trifluoroethyl ether (THE), Methoxyperfluorobutane (MPB), Bis(2,2-difluoroethyl) ether (DFE), 2,2,2-Trifluoroethyl methyl ether (TFEME), Bis(2-fluoroethyl) ether (B) FE), bis(2,2,2,trifluoroethyl) ether (BTFE), 3-fluoropyridine (3FP), 1,2-(1,1,2,2-tetrafluoroethoxy)ethane (TFEE), 1,2-dimethoxy-1,1,2,2-tetrafluoroethane (DMETF), 2-methyl-1(1,1,2,2-tetrafluoroethoxy)propane (TFEIBE), bis(2,2,3,3,3-pentafluoropropyl) ether (BPFPE), allyl 2,2,3,3,3-pentafluoropropyl ether (APFPE), hydrocarbons and combinations thereof.

23. The electrolyte system of claim 21, wherein the at least one solvent is present in a cumulative amount ranging from more than 0% by volume to about 75% by volume of the electrolyte system.

24. The electrolyte system of claim 21, wherein the at least one electron-withdrawing compound comprises at least one α-hydrogenated selectively β-modified moiety.

25. The electrolyte system of claim 24, wherein the at least one α-hydrogenated selective β-modified unit does not include fluorine.

26. The electrolyte system of claim 21, wherein the at least one electron-withdrawing compound does not include fluorine.

27. The electrolyte system of claim 21, wherein the at least one electron-withdrawing compound is selected from: 2,2-dimethoxy-4-trifluoromethyl-1,3-dioxolane (DTDL), 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG), 1,1,1,14,14,14-hexafluoro-3,6,9,12-tetraoxatetradecane (FTrG), 1,1,1,17,17,17-hexafluoro-3,6,9,12,15-pentaheptadecane (FTeG), bis(2,2-difluoroethyl) ether (BDE), bis(2,2,2,trifluoroethyl) ether (BTF) E), 2,2,2-trifluoroethyl-2-fluoroethyl ether (TFFE), 1,1-difluoroethyl-2-fluoroethyl ether (DFE), fluorinated 1,4-dimethoxybutane (FDMB), 3-fluoropyridine (3FP), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,3,3-tetrafluoropropyl) ether (BTFPE), 2,2,2-trifluoroethyl-1,1,2,2-tetrafluoroethyl ether (TFTFE), tris(2,2,2-trifluoroethyl) phosphate, bis(2,2,2-trifluoroethyl) methylphosphonate, isosorbide dinitrate (ISDN), bis(2-fluoroethyl) ether (BFE), and combinations thereof.

28. The electrolyte system of claim 21, wherein the at least one electron-withdrawing compound is present in an accumulated amount ranging from more than 0% by volume to about 75% by volume of the electrolyte system.

29. The electrolyte system of claim 21, wherein the at least one lithium-ion transport compound is selected from: lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO3), lithium perchlorate (LiClO4), lithium difluoro(oxaloyl)borate (LiFOB), lithium bis(oxaloyl)borate (LiBOB), lithium trifluoromethanesulfonate (LiTf), lithium bis(pentafluoroethanesulfonyl)imide (LiBETi), lithium bis(fluorosulfonyl)imide (LiFSI), lithium trifluoroacetate (LiTFAc), and combinations thereof.

30. The electrolyte system of claim 21, wherein the at least one lithium-ion transport compound is present in an amount ranging from about 0.1 M to about 10 M.

31. The electrolyte system of claim 30, wherein the at least one chalcogenide is selected from: dimethyl diselenyl ether (DMDSe), diphenyl diselenyl ether (DPDSe), dimethyl ditelluride (DMDTe), diphenyl ditelluride (DPDTe), and combinations thereof.

32. The electrolyte system of claim 31, wherein the at least one chalcogenide is present in a cumulative amount ranging from about 0.1% by weight to about 3.0% by weight.

33. An electrochemical single-cell battery comprising the electrolyte system as described in claim 21.

34. The electrochemical single cell battery of claim 33, wherein the electrochemical single cell battery is characterized by a coin-like structure.

35. The electrochemical single cell according to claim 33, wherein the electrochemical single cell is characterized by a cylindrical structure.

36. The electrochemical single cell according to claim 33, wherein the electrochemical single cell is characterized by a prismatic structure.

37. The electrochemical single cell according to claim 33, wherein the electrochemical single cell is characterized by a pouch structure.

38. The electrochemical single cell of claim 33, wherein the electrochemical single cell neither includes nor is coupled to any different structure used as a current collector.

39. An electrolyte system comprising: Solvent system; At least one electron-withdrawing compound; and At least one lithium-ion transport compound.

40. The electrolyte system of claim 39, wherein the solvent system comprises at least one solvent selected from the group consisting of: dimethoxyethane (DME), dioxolane (DOL), dimethyl sulfoxide (DMSO), dimethylformamide (DMF), toluene, tetramethylurea (TMU), tetrabutylammonium hydroxide (TBA), dimethylacetamide (DMA), tetrahydrofuran (THF), diethylene glycol dimethyl ether (diethylene glycol dimethyl ether or DEGDME), acetonitrile (ACN), dimethyl trisulfide (DMTS), and diisopropyl ether. (DIPE), tetrahydrofuran (THF), 1,2-diaminopropane (DAP), triethylene glycol dimethyl ether (trigDME), tetraethylene glycol dimethyl ether (TEGDME), sulfolane (SUL), methyl tert-butyl ether (MTBE), 2,2,3,3-tetrafluoro-1,4-dimethoxybutane (FDMB), bis(2,2,2,trifluoroethyl) ether (BTFE), 1H,1H,5H-octafluoropentyl 1,1,2,2-tetrafluoroethyl ether (OFE), ( 1,1,2,2-Tetrafluoroethyl 2,2,3,3-Tetrafluoropropyl ether (TTE), 2,2,2-Trifluoroethyl 1,1,2,2-Tetrafluoroethyl ether (TFETFE), 1,1,2,2-Tetrafluoroethyl isobutyl ether (TFEIE), 1,1,2,3,3,3-Hexafluoropropyl 2,2,2-Trifluoroethyl ether (THE), Methoxyperfluorobutane (MPB), Bis(2,2-difluoroethyl) ether (DFE), 2,2,2-Trifluoroethyl methyl ether (TFEME), Bis(2-fluoroethyl) ether (B) FE), bis(2,2,2,trifluoroethyl) ether (BTFE), 3-fluoropyridine (3FP), 1,2-(1,1,2,2-tetrafluoroethoxy)ethane (TFEE), 1,2-dimethoxy-1,1,2,2-tetrafluoroethane (DMETF), 2-methyl-1(1,1,2,2-tetrafluoroethoxy)propane (TFEIBE), bis(2,2,3,3,3-pentafluoropropyl) ether (BPFPE), allyl 2,2,3,3,3-pentafluoropropyl ether (APFPE), hydrocarbons and combinations thereof.

41. The electrolyte system of claim 39, wherein the solvent system comprises more than 0% by volume of the electrolyte system to about 75% by volume of the electrolyte system.

42. The electrolyte system of claim 39, wherein the at least one electron-withdrawing compound is selected from: 2,2-dimethoxy-4-trifluoromethyl-1,3-dioxolane (DTDL), 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG), 1,1,1,14,14,14-hexafluoro-3,6,9,12-tetraoxatetradecane (FTrG), 1,1,1,17,17,17-hexafluoro-3,6,9,12,15-pentaheptadecane (FTeG), bis(2,2-difluoroethyl) ether (BDE), bis(2,2,2,trifluoroethyl) ether (BTF) E), 2,2,2-trifluoroethyl-2-fluoroethyl ether (TFFE), 1,1-difluoroethyl-2-fluoroethyl ether (DFE), fluorinated 1,4-dimethoxybutane (FDMB), 3-fluoropyridine (3FP), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,3,3-tetrafluoropropyl) ether (BTFPE), 2,2,2-trifluoroethyl-1,1,2,2-tetrafluoroethyl ether (TFTFE), tris(2,2,2-trifluoroethyl) phosphate, bis(2,2,2-trifluoroethyl) methylphosphonate, isosorbide dinitrate (ISDN), bis(2-fluoroethyl) ether (BFE), and combinations thereof.

43. The electrolyte system of claim 39, wherein the at least one electron-withdrawing compound is present in an accumulated amount ranging from more than 0% by volume to about 75% by volume of the electrolyte system.

44. The electrolyte system of claim 39, wherein the at least one electron-withdrawing compound comprises at least one α-hydrogenated selectively β-modified moiety.

45. The electrolyte system of claim 39, wherein the at least one α-hydrogenated selective β-modified unit does not include fluorine.

46. ​​The electrolyte system of claim 39, wherein the at least one electron-withdrawing compound does not include fluorine.

47. The electrolyte system of claim 39, wherein the at least one lithium-ion transport compound is selected from: lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), lithium nitrate (LiNO3), lithium perchlorate (LiClO4), lithium difluoro(oxaloyl)borate (LiFOB), lithium bis(oxaloyl)borate (LiBOB), lithium trifluoromethanesulfonate (LiTf), lithium bis(pentafluoroethanesulfonyl)imide (LiBETi), lithium bis(fluorosulfonyl)imide (LiFSI), lithium trifluoroacetate (LiTFAc), and combinations thereof.

48. The electrolyte system of claim 39, wherein the lithium-ion transport compound is present in an amount ranging from about 0.1 M to about 10 M.

49. An electrochemical single-cell battery comprising: the electrolyte system as described in claim 39.

50. The electrochemical single cell of claim 49, wherein the electrochemical single cell is characterized by a coin-like construction.

51. The electrochemical single cell of claim 49, wherein the electrochemical single cell is characterized by a cylindrical structure.

52. The electrochemical single cell of claim 49, wherein the electrochemical single cell is characterized by a prismatic structure.

53. The electrochemical single cell of claim 49, wherein the electrochemical single cell is characterized by a pouch structure.

54. A lithium-based anode comprising: The interface phase formed on the surface of the lithium-based anode, The interface phase is formed by the interaction between the active material of the lithium-based anode and a derivative of at least one electron-withdrawing compound.

55. The lithium-based anode of claim 54, wherein the at least one electron-withdrawing compound comprises at least one α-hydrogenated selectively β-modified moiety.

56. The lithium-based anode of claim 55, wherein the at least one α-hydrogenated selective β-modified moiety does not include fluorine.

57. The lithium-based anode of claim 54, wherein the electron-withdrawing compound does not include fluorine.

58. The lithium-based anode of claim 54, wherein the at least one electron-withdrawing compound is selected from: 2,2-dimethoxy-4-trifluoromethyl-1,3-dioxolane (DTDL), 1,1,1-trifluoro-2-(2-(2-(2,2,2-trifluoroethoxy)ethoxy)ethoxy)ethane (FDG), 1,1,1,14,14,14-hexafluoro-3,6,9,12-tetraoxatetradecane (FTrG), 1,1,1,17,17,17-hexafluoro-3,6,9,12,15-pentaheptadecane (FTeG), bis(2,2-difluoroethyl) ether (BDE), bis(2,2,2,trifluoroethyl) ether (BTFE) ), 2,2,2-trifluoroethyl-2-fluoroethyl ether (TFFE), 1,1-difluoroethyl-2-fluoroethyl ether (DFE), fluorinated 1,4-dimethoxybutane (FDMB), 3-fluoropyridine (3FP), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), bis(2,2,3,3-tetrafluoropropyl) ether (BTFPE), 2,2,2-trifluoroethyl-1,1,2,2-tetrafluoroethyl ether (TFTFE), tris(2,2,2-trifluoroethyl) phosphate, bis(2,2,2-trifluoroethyl) methylphosphonate, isosorbide dinitrate (ISDN), bis(2-fluoroethyl) ether (BFE), and combinations thereof.

59. The lithium-based anode of claim 54, wherein the active material of the lithium-based anode comprises elemental lithium or a lithium alloy.

60. The lithium-based anode of claim 59, wherein the lithium alloy comprises lithium-magnesium, lithium-sulfur, or a combination thereof.

61. An electrochemical single-cell battery comprising the lithium-based anode as described in claim 54.

62. The electrochemical single cell according to claim 61, wherein the electrochemical single cell is characterized by a coin-like structure.

63. The electrochemical single cell according to claim 61, wherein the electrochemical single cell is characterized by a cylindrical structure.

64. The electrochemical single cell according to claim 61, wherein the electrochemical single cell is characterized by a prismatic structure.

65. The electrochemical single cell of claim 61, wherein the electrochemical single cell is characterized by a pouch structure.

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