Battery compositions and methods of making and using

Abstract

Herein disclosed is an electrochemical device. The device includes an anode, a cathode, and an electrolyte. The cathode includes lithium manganese iron phosphate (LiMnxFe1-xPO4, LMFP) or sodium manganese iron phosphate (NaMnxFe1-xPO4, NMFP), or potassium manganese iron phosphate (KMnxFe1-xPO4, KMFP). The electrolyte includes a solvent comprising N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA) or Dimethylsulfamoyl fluoride (DMSF). Methods of making and using such a device are also disclosed.

Description

Atty. Dkt. No.142193-0122 (EM2402PCT) BATTERY COMPOSITIONS AND METHODS OF MAKING AND USING CROSS-REFERENCE TO RELATED APPLICATION

[0001] The present application claims the benefit of priority to U.S. Provisional Application No. 63 / 690,033, filed September 3, 2024, the entire content of which is incorporated herein by reference. BACKGROUND

[0002] Lithium-ion batteries (LIBs) are pivotal in today’s energy storage technologies, powering everything from portable electronics to electric vehicles (EVs) and grid storage solutions. SUMMARY

[0003] At least one aspect of the present disclosure is directed to an electrochemical device including an anode, a cathode, and an electrolyte. The cathode includes lithium manganese iron phosphate (LiMnxFe1-xPO4, LMFP) or sodium manganese iron phosphate (NaMnxFe1-xPO4, NMFP), or potassium manganese iron phosphate (KMnxFe1-xPO4, KMFP). The electrolyte includes a solvent including N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA) or Dimethylsulfamoyl fluoride (DMSF).

[0004] In an embodiment, the electrolyte includes lithium bis(fluorosulfonyl)imide (LiFSI) or lithium hexafluorophosphate (LiPF6) substantially dissolved in the solvent. In an embodiment, the LiFSI or LiPF6 is present at a concentration of about 0.2 to about 5.0 moles of LiFSI or LiPF6 per kilogram of DMTMSA or DMSF or at a concentration of about 1.0 mole to about 2.0 moles of LiFSI or LiPF6 per kilogram of DMTMSA. In an embodiment, the LiFSI or LiPF6 is present in the electrolyte in a weight percent of from about 1% to about 30% of the electrolyte or in a weight percent of from about 5% to about 20% of the electrolyte.

[0005] In an embodiment, a content of manganese (x) in LMFP, or in NMPF, or in KMFP is 0, or 1, or between 0 and 1, or from 0.4 to 0.8, or from 0.6 to 0.8. In an embodiment, the solvent also includes a linear carbonate, ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), or combinations thereof.

[0006] In an embodiment, the electrolyte additionally includes at least one of: fluoroethylene carbonate (FEC), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), prop-1-ene-1,3-sultone (PST), vinylene carbonate (VC), ethylene carbonate (EC), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), 1 4910-0922-0703.2Atty. Dkt. No.142193-0122 (EM2402PCT) tris(trimethylsilyl)phosphite (TMSPi), Lithium Difluorophosphate (LiDFP), 1,3,2- Dioxathiolane 2,2-dioxide (DTD), Lithium Tetrafluoro Oxalato Phosphate (LiTFOP). In an embodiment, the electrolyte includes from 0.25 wt% to 5 wt% vinylene carbonate. In an embodiment, the electrolyte includes no greater than 8 wt% fluoroethylene carbonate (FEC) and wherein the electrolyte includes no greater than 15 wt% ethylene carbonate (EC) or no greater than 8 wt% ethylene carbonate (EC).

[0007] In an embodiment, the electrolyte includes no less than 1.25 wt% of 1,1,2,2- tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), vinylene carbonate (VC), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), tris(trimethylsilyl)phosphite (TMSPi), Lithium Difluorophosphate (LiDFP), 1,3,2- Dioxathiolane 2,2-dioxide (DTD), 1,3-propanesultone, Lithium Tetrafluoro Oxalato Phosphate (LiTFOP), or any combination thereof. In an embodiment, the electrolyte includes at least 20 wt% of DMSF or DMTMSA.

[0008] In an embodiment, the anode includes hard carbon, or graphite, or silicon, or combinations thereof. In an embodiment, the cathode includes 100 wt% of LMFP or NMFP or KMFP, or wherein the cathode includes from 70 wt% to 30 wt% of LMFP or NMFP or KMFP. In an embodiment, the cathode also includes from 30 wt% to 70 wt% of a compound of nickel manganese cobalt oxides (LiNixMnyCo1-x-yO2, NMC) or of lithium nickel cobalt aluminum oxides (LiNixCoyAl1-x-yO2, NCA).

[0009] In an embodiment, the cathode includes metal oxides, metal sulfates, metal phosphates, metal silicates, sulfur, or combinations thereof. In an embodiment, the cathode includes lithium cobalt oxide (LiCoO2), lithium manganese oxide (LiMn2O4), lithium nickel manganese oxide (LiNixMnyO2, LNMO), lithium iron phosphate (LiFePO4, or LFP), lithium nickel manganese cobalt oxide (LiNixMnyCo1-x-yO2 or NMC), lithium nickel cobalt aluminium oxides (LiNixCoyAl1-x-yO2, NCA), or sodium vanadium phosphate Na3V2(PO4)3, or sodium nickel iron manganese oxide (NaNixFeyMn1-x-yO2), or combinations thereof.

[0010] In an embodiment, the device is configured to operate at a temperature in a range of from -30 degrees C to 65 degrees C. In an embodiment, the device is configured to operate at a voltage of up to 4.7V, or up to 4.55V, or up to 4.4 V, or up to 4.3V, or up to 4.2V, or up to 3.8V, or up to 3.7V. In an embodiment, the device is configured to retain at least 80% capacity after 500 cycles, or after 1000 cycles, or after 2000 cycles, or after 5000 cycles. 2 4910-0922-0703.2Atty. Dkt. No.142193-0122 (EM2402PCT)

[0011] At least one aspect of the present disclosure is directed to a method of making an electrochemical device, wherein the method includes providing an anode, a cathode, and an electrolyte, wherein the cathode includes lithium manganese iron phosphate (LMFP) or sodium manganese iron phosphate (NMFP), or potassium manganese iron phosphate (KMFP), and wherein the electrolyte includes a solvent including N, N-dimethyltrifluoromethane- sulfonamide (DMTMSA) or Dimethylsulfamoyl fluoride (DMSF). In an embodiment, the electrolyte includes lithium bis(fluorosulfonyl)imide (LiFSI) or lithium hexafluorophosphate (LiPF6) substantially dissolved in the solvent.

[0012] Further discussed herein is a method of using an electrochemical device, wherein the method includes providing an anode, a cathode, and an electrolyte, wherein the cathode includes lithium manganese iron phosphate (LMFP) or sodium manganese iron phosphate (NMFP), or potassium manganese iron phosphate (KMFP), and wherein the electrolyte includes a solvent including N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA) or Dimethylsulfamoyl fluoride (DMSF). In an embodiment, the electrolyte includes lithium bis(fluorosulfonyl)imide (LiFSI) or lithium hexafluorophosphate (LiPF6) substantially dissolved in the solvent. In an embodiment, the device operates at a temperature in a range of from -30 degrees C to 65 degrees C. In an embodiment, the device operates at a voltage of up to 4.7V, or up to 4.55V, or up to 4.4 V, or up to 4.3V, or up to 4.2V, or up to 3.8V, or up to 3.7V. In an embodiment, the device retains at least 80% capacity after 500 cycles, or after 1000 cycles, or after 2000 cycles, or after 5000 cycles.

[0013] All combinations of the foregoing concepts and additional concepts discussed in greater detail below (provided such concepts are not mutually inconsistent) are part of the inventive subject matter disclosed herein. In particular, all combinations of claimed subject matter appearing at the end of this disclosure are part of the inventive subject matter disclosed herein. The terminology used herein that also may appear in any disclosure incorporated by reference should be accorded a meaning most consistent with the particular concepts disclosed herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] The following drawings are provided to illustrate certain embodiments described herein. The drawings are merely illustrative and are not intended to limit the scope of claimed inventions and are not intended to show every potential feature or embodiment of the claimed inventions. The drawings are not necessarily drawn to scale; in some instances, 3 4910-0922-0703.2Atty. Dkt. No.142193-0122 (EM2402PCT) certain elements of the drawing may be enlarged with respect to other elements of the drawing for purposes of illustration.

[0015] FIG.1 is a plot that compares the capacity retention of a control AG / LMFP battery with that of a battery of this disclosure, according to an embodiment of this disclosure.

[0016] FIG.2 is a plot that compares the direct current internal resistance of a control battery with that of a battery of this disclosure, according to an embodiment of this disclosure. DETAILED DESCRIPTION

[0017] Overview. The dominance of lithium ion batteries can be attributed to high energy density, long cycle life, and relatively low self-discharge rates. Despite these advantages, several challenges persist, especially when it comes to cathode materials and the desire to operate at higher voltages and energy densities.

[0018] Clearly, there is continuing need and interest to develop improved energy storage devices. This disclosure discusses battery compositions that allow for the use of new and emerging cathode materials and that enhance battery performances, such as operating voltages and battery capacities after many cycles.

[0019] The overall performance of LIBs is often determined by cathode materials in the batteries. The most common cathode materials include lithium cobalt oxide (LiCoO₂), lithium manganese oxide (LiMn₂O₄), lithium nickel manganese cobalt oxide (NMC), and lithium iron phosphate (LiFePO₄). Each of these materials faces specific challenges. For example, LiCoO₂ is prone to capacity fading and thermal instability, which can lead to safety concerns. LiMn₂O₄ suffers from Jahn-Teller distortion, which causes capacity fading during cycling. In NMC, there is a complex balance in the ratio of nickel, manganese, and cobalt to optimize capacity, stability, and cost. LiFePO₄ has excellent thermal stability and cycle life but lower energy density compared to other materials.

[0020] In addition, the interface between the cathode and electrolyte can be a critical area where reactions can lead to performance degradation. At high voltages, common electrolyte solvents (e.g., ethylene carbonate, dimethyl carbonate) tend to decompose, forming a solid-electrolyte interphase layer that can impede lithium-ion transport. This degradation is exacerbated at elevated temperatures, leading to accelerated capacity loss and safety hazards.

[0021] Cathode materials, particularly those containing manganese (e.g., LiMn₂O₄), can suffer from the dissolution of transition metals into the electrolyte. This not only depletes 4 4910-0922-0703.2Atty. Dkt. No.142193-0122 (EM2402PCT) the active material but also contaminates the electrolyte, further degrading battery performance. Strategies to mitigate this problem include coating the cathode material and optimizing the electrolyte composition.

[0022] To achieve higher energy densities, the batteries can be operated at higher voltages. However, conventional electrolytes can break down at these higher voltages, leading to severe capacity fading and safety issues. High-voltage operation may require improved compatibility between the electrode and electrolyte. For instance, high-nickel cathodes can offer higher capacities but can require electrolytes that can withstand the oxidative environment at higher voltages. This compatibility can be crucial to ensure long-term stability and performance. Higher energy densities can often result in increased mechanical stress within the battery cells due to volumetric changes during lithium insertion and extraction. This stress can lead to micro-cracking of the electrodes, exacerbating capacity loss and safety risks.

[0023] Lithium Manganese Iron Phosphate (LMFP) Cathode Materials. LMFP (LiMnxFe1-xPO4) is an emerging cathode material that combines the advantages of LiFePO4 and LiMn2O4. It aims to leverage the high thermal stability and safety of LiFePO4 with the higher voltage and capacity potential of manganese-based materials. In this disclosure, LMFP is often used as examples; but sodium manganese iron phosphate (NaMnxFe1-xPO4, NMFP) and potassium manganese iron phosphate (KMnxFe1-xPO4, KMFP) are also contemplated and are interchangeable with LMFP unless otherwise specified. Notably, LFP and LMFP are not transition metal oxides. Similarly, NMFP and KMFP also are not transition metal oxides.

[0024] In various embodiments, the LMFP cathode is synthesized via various methods, such as solid-state reactions, sol-gel processes, hydrothermal methods. In various embodiments, the LMFP is doped with other elements (e.g., Mg, Al) and / or coated with conductive materials (e.g., carbon) to enhance its electrical conductivity and structural stability.

[0025] In various embodiments, LMFP particle size and morphology is controlled to adjust its electrochemical performance. For example, nano-sized LMFP particles with well- defined morphologies improve the rate capability and cycle life.

[0026] The use of LMFP in the cathode is not without challenges. For example, LMFP, like LiFePO₄, can suffer from low intrinsic electrical conductivity. In addition, achieving high- rate capability while maintaining capacity and cycle life can be a significant problem. Furthermore, ensuring long-term cycling stability, especially under high-rate and high-voltage 5 4910-0922-0703.2Atty. Dkt. No.142193-0122 (EM2402PCT) conditions, can be difficult. In some embodiments, the structural integrity of LMFP must also be maintained to prevent capacity fading after many cycles.

[0027] Battery Compositions. It has been unexpectedly discovered that an electrolyte including a solvent including N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA, i.e., C3H6F3NO2S) or Dimethylsulfamoyl fluoride (DMSF, i.e., FSO2NC2H6) allows for the use of LMFP cathode materials (and the like) and mitigates many associated challenges. In an embodiment, an electrochemical device includes: an anode, a cathode, and an electrolyte, wherein the cathode includes lithium manganese iron phosphate (LMFP) or sodium manganese iron phosphate (NMFP), or potassium manganese iron phosphate (KMFP), and wherein the electrolyte includes a solvent including N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA) or Dimethylsulfamoyl fluoride (DMSF). In an embodiment, the electrolyte includes lithium bis(fluorosulfonyl)imide (LiFSI) or lithium hexafluorophosphate (LiPF6) substantially dissolved in the solvent.

[0028] In an embodiment, the LiFSI or LiPF6 is present at a concentration of about 0.2 to about 5.0 moles of LiFSI or LiPF6 per kilogram of DMTMSA or DMSF or at a concentration of about 1.0 mole to about 2.0 moles of LiFSI or LiPF6 per kilogram of DMTMSA or DMSF. In an embodiment, the LiFSI or LiPF6 is present in the electrolyte in a weight percent of about 1% to about 30% of the electrolyte or in a weight percent of about 5% to about 20% of the electrolyte.

[0029] In an embodiment, the anode includes lithium metal, or sodium metal, or potassium metal, or hard carbon, or graphite, or silicon, or combinations thereof. In an embodiment, the cathode includes 100 wt% of LMFP or NMFP or KMFP, or wherein the cathode includes 70 wt% to 30 wt% of LMFP or NMFP or KMFP. In an embodiment, the cathode also includes 30 wt% to 70 wt% of a compound of nickel manganese cobalt oxide (NMC).

[0030] In an embodiment, a content of manganese (x) in LMFP, or in NMPF, or in KMFP is 0, or 1, or between 0 and 1, or from 0.4 to 0.8, or from 0.6 to 0.8. In an embodiment, the solvent also includes a linear carbonate, ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), or combinations thereof.

[0031] In an embodiment, the electrolyte additionally includes at least one of: fluoroethylene carbonate (FEC), 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), prop-1-ene-1,3-sultone (PST), vinylene carbonate (VC), ethylene carbonate (EC), 6 4910-0922-0703.2Atty. Dkt. No.142193-0122 (EM2402PCT) lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), tris(trimethylsilyl)phosphite (TMSPi), Lithium difluorophosphate (LiDFP), tris(trimethylsilyl)phosphite (TMSPi), tris(trimethylsilyl)borate (TMSB), or tris(trimethylsilyl)phosphate (TMSP). In an embodiment, the electrolyte includes from 0.25 wt% to 5 wt% vinylene carbonate. In an embodiment, the electrolyte includes no greater than 8 wt% fluoroethylene carbonate (FEC) and wherein the electrolyte includes no greater than 15 wt% ethylene carbonate (EC) or no greater than 8 wt% ethylene carbonate (EC).

[0032] In an embodiment, the electrolyte includes no less than 1.25 wt% of 1,1,2,2- tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), vinylene carbonate (VC), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), tris(trimethylsilyl)phosphite (TMSPi), Lithium Difluorophosphate (LiDFP), 1,3,2- Dioxathiolane 2,2-dioxide (DTD), 1,3-propanesultone, Lithium Tetrafluoro Oxalato Phosphate (LiTFOP), or any combination thereof. In an embodiment, the electrolyte includes at least 20 wt% of DMSF or DMTMSA.

[0033] In an embodiment, the anode includes hard carbon, or graphite, or silicon, or combinations thereof. In an embodiment, the cathode includes 100 wt% of LMFP or NMFP or KMFP, or wherein the cathode includes from 70 wt% to 30 wt% of LMFP or NMFP or KMFP. In an embodiment, the cathode also includes from 30 wt% to 70 wt% of a compound of nickel manganese cobalt oxides (LiNixMnyCo1-x-yO2, NMC) or of lithium nickel cobalt aluminum oxides (LiNixCoyAl1-x-yO2, NCA).

[0034] In an embodiment, the cathode includes metal oxides, metal sulfates, metal phosphates, metal silicates, sulfur, or combinations thereof. In an embodiment, the cathode includes lithium cobalt oxide (LiCoO2), lithium manganese oxide (LiMn2O4), lithium iron phosphate (LiFePO4 or LFP), lithium nickel manganese cobalt oxide (LiNiMnCoO2 or NMC), or sodium vanadium phosphate Na3V2(PO4)3, or combinations thereof. In an embodiment, the cathode includes lithium cobalt oxide (LiCoO2), lithium manganese oxide (LiMn2O4), lithium nickel manganese oxide (LiNixMnyO2, LNMO), lithium iron phosphate (LiFePO4, or LFP), lithium nickel manganese cobalt oxide (LiNixMnyCo1-x-yO2 or NMC), lithium nickel cobalt aluminium oxides (LiNixCoyAl1-x-yO2, NCA), or sodium vanadium phosphate Na3V2(PO4)3, or sodium nickel iron manganese oxide (NaNixFeyMn1-x-yO2), or combinations thereof.

[0035] In various embodiments, the device of this disclosure is operable at a temperature in a range of from -30 degrees C to 60 degrees C. In various embodiments, the 7 4910-0922-0703.2Atty. Dkt. No.142193-0122 (EM2402PCT) device of this disclosure is operable at atmospheric pressure or within 20% above or below such pressure.

[0036] In various embodiments, the device of this disclosure is operable at a voltage of up to 4.5V, or up to 4.4V, or up to 4.3V, or up to 4.4V, or up to 4.2V, or up to 3.8V, or up to 3.7V. In an embodiment, the device is configured to operate at a temperature in a range of from -30 degrees C to 65 degrees C. In an embodiment, the device is configured to operate at a voltage of up to 4.7V, or up to 4.55V, or up to 4.4 V, or up to 4.3V, or up to 4.2V, or up to 3.8V, or up to 3.7V. In various embodiments, the device of this disclosure is able to retain at least 80% capacity after 500 cycles, or after 1000 cycles, or after 2000 cycles, or after 5000 cycles.

[0037] In another embodiment, a method of making an electrochemical device includes providing an anode, a cathode, and an electrolyte, wherein the cathode includes lithium manganese iron phosphate (LMFP) or sodium manganese iron phosphate (NMFP), or potassium manganese iron phosphate (KMFP), and wherein the electrolyte includes a solvent including N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA) or Dimethylsulfamoyl fluoride (DMSF). In an embodiment, the electrolyte includes lithium bis(fluorosulfonyl)imide (LiFSI) or lithium hexafluorophosphate (LiPF6) substantially dissolved in the solvent.

[0038] In a further embodiment, a method of using an electrochemical device includes providing an anode, a cathode, and an electrolyte, wherein the cathode includes lithium manganese iron phosphate (LMFP) or sodium manganese iron phosphate (NMFP), or potassium manganese iron phosphate (KMFP), and wherein the electrolyte includes a solvent including N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA) or Dimethylsulfamoyl fluoride (DMSF). In an embodiment, the electrolyte includes lithium bis(fluorosulfonyl)imide (LiFSI) or lithium hexafluorophosphate (LiPF6) substantially dissolved in the solvent.

[0039] In an embodiment, the device operates at a temperature in a range of from -30 degrees C to 60 degrees C. In an embodiment, the device operates at a voltage of up to 4.5V, or up to 4.3V, or up to 4.2V, or up to 3.8V, or up to 3.7V. In an embodiment, the device retains at least 80% capacity after 500 cycles, or after 1000 cycles, or after 2000 cycles, or after 5000 cycles.

[0040] Without wishing to be limited by any theory, the battery compositions of this disclosure have at least one or more of these technical characteristics when compared with conventional LIBs. (1) Higher operating voltages of LMFP cathodes (e.g., up to 4.5V) often 8 4910-0922-0703.2Atty. Dkt. No.142193-0122 (EM2402PCT) lead to increased decomposition of the electrolyte, resulting in the formation of an unstable solid electrolyte interphase (SEI) layer. This causes increased resistance and reduced battery life. DMTMSA or DMSF in the electrolyte used in combination with the cathode as taught in this disclosure instead forms a very stable SEI layer, i.e., technically a CEI layer (Cathode Electrolyte Interface), such that it does not decompose under higher voltages of operation. (2) At higher voltages, manganese often dissolves from the cathode into the electrolyte. This not only depletes the active material in the cathode but also leads to detrimental effects in the anode, further accelerating capacity fade. Surprisingly, it has been discovered that DMTMSA or DMSF prevents manganese dissolution. (3) The mechanical stresses induced during cycling often lead to the fracture of LMFP particles, which then compromises the structural integrity and leads to capacity loss. Surprisingly, it was discovered that DMTMSA or DMSF stabilizes the LMFP particles and prevents cyclic stress induced failure.

[0041] Advantages. LFP in traditional batteries is limited with an operating voltage of up to 3.65V or up to 3.7V. The battery compositions of this disclosure allow for higher operation voltages. Furthermore, surprisingly the solvent of this disclosure in the electrolyte mitigates many of the failure mechanisms of LMFP-containing cathodes, such as prevention of transition metal dissolution, reduction of oxygen formation, reduction of HF formation, prevention of cathode-electrolyte reactions, stabilization of cathode-electrolyte interface. Additionally, it has been unexpectedly discovered that the cycle life of a battery with LMFP or KMFP or NMFP in the cathode and DMTMSA or DMSF in the electrolyte is more than 10 times longer than conventional electrolytes with LMFP cathode. Economically, the use of LMFP or NMFP or KMFP in the cathode eliminates the need of expensive metals like cobalt and nickel. Furthermore, it allows for the batteries to be operated at substantially higher voltages and energy densities than LFP cathode while allowing the use of low-cost materials with more domestic supply chain availability. EXAMPLES

[0042] The following examples are provided as part of the disclosure of various embodiments of the present invention. As such, none of the information provided below is to be taken as limiting the scope of the invention.

[0043] Example 1. A control battery containing a lithium metal anode, a LMFP cathode (LiMn0.6Fe0.4PO4), and a conventional LP57 electrolyte (1 Molality lithium hexafluorophosphate LiPF6 in a mixture of ethylene carbonate and ethyl methyl carbonate) 9 4910-0922-0703.2Atty. Dkt. No.142193-0122 (EM2402PCT) was cycled between 4.5V and 3V. After 20 cycles, the control battery capacity was less than 78%. A battery according to this disclosure, containing a lithium metal anode, a LMFP cathode (LiMn0.6Fe0.4PO4), and an electrolyte having 1 Molality LiFSI in DMTMSA, was also cycled between 4.5V and 3V. After 20 cycles, the capacity of the battery according to this disclosure was greater than 99%.

[0044] Example 2. FIG. 1 is a plot that compares the capacity retention of a control AG / LMFP battery with that of a battery of this disclosure. As shown in FIG.1, two identical dry pouch cell batteries are filled with different electrolytes and cycled between 2.8V and 4.3V at a rate of 1C charge and 1C discharge. Both 1 amp-hour batteries contain a graphite anode and an LMFP cathode (LiMn0.7Fe0.3PO4) and are loaded at 1.93 mAh / cm2. The control battery is filled with a state-of-the-art, carbonate-based commercial electrolyte and exhibits a capacity retention of roughly 94% after 600 cycles with a projected cycle life of approximately 2500 cycles to 80% capacity retention. The battery according to this disclosure is filled with a carbonate-based electrolyte including dimethylsulfamoyl fluoride (DMSF) and exhibits a capacity retention of nearly 98% after 600 cycles with a projected cycle life of over 5,000 cycles to 80% capacity retention.

[0045] Example 3. FIG. 2 is a plot that compares the DCIR (Direct Current Internal Resistance) of a control battery with that of a battery of this disclosure. As shown in FIG.2, two identical dry pouch cell batteries are filled with different electrolytes and cycled between 2.8V and 4.3V at a rate of 1C charge and 1C discharge. Both 1 amp-hour batteries contain a graphite anode and an LMFP cathode (LiMn0.7Fe0.3PO4) and are loaded at 1.93 mAh / cm2. The control battery is filled with a state-of-the-art, carbonate-based commercial electrolyte and exhibits more than a 45% increase in DCIR over 750 cycles. The battery according to this disclosure is filled with a carbonate-based electrolyte including dimethylsulfamoyl fluoride (DMSF) and exhibits less than 8% increase in DCIR over 750 cycles. As known to one skilled in the art, DCIR is a measure of a battery's opposition to direct current flow, indicating energy loss and battery health. A higher DCIR suggests a less efficient battery, while a lower DCIR indicates better performance, making it a critical parameter for assessing battery quality and predicting its lifespan. Clearly, the battery of this disclosure is far superior to the control battery.

[0046] While various inventive embodiments have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and / or structures for performing the function and / or obtaining the results and / or one or more of the 10 4910-0922-0703.2Atty. Dkt. No.142193-0122 (EM2402PCT) advantages described herein, and each of such variations and / or modifications is deemed to be within the scope of the inventive embodiments described herein. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and / or configurations will depend upon the specific application or applications for which the inventive teachings is / are used. Those skilled in the art will recognize or be able to ascertain, using no more than routine experimentation, many equivalents to the specific inventive embodiments described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, inventive embodiments may be practiced otherwise than as specifically described and claimed. Inventive embodiments of the present disclosure are directed to each individual feature, system, article, material, kit, and / or method described herein. In addition, any combination of two or more such features, systems, articles, materials, kits, and / or methods, if such features, systems, articles, materials, kits, and / or methods are not mutually inconsistent, is included within the inventive scope of the present disclosure.

[0047] Also, various inventive concepts may be embodied as one or more methods, of which an example has been provided. The acts performed as part of the method may be ordered in any suitable way. Accordingly, embodiments may be constructed in which acts are performed in an order different than illustrated, which may include performing some acts simultaneously, even though shown as sequential acts in illustrative embodiments.

[0048] All definitions, as defined and used herein, should be understood to control over dictionary definitions, definitions in documents incorporated by reference, and / or ordinary meanings of the defined terms. The indefinite articles “a” and “an,” as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.”

[0049] The phrase “and / or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Multiple elements listed with “and / or” should be construed in the same fashion, i.e., “one or more” of the elements so conjoined. Other elements may optionally be present other than the elements specifically identified by the “and / or” clause, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, a reference to “A and / or B”, when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to 11 4910-0922-0703.2Atty. Dkt. No.142193-0122 (EM2402PCT) A only (optionally including elements other than B); in another embodiment, to B only (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.

[0050] As used herein in the specification and in the claims, “or” should be understood to have the same meaning as “and / or” as defined above. For example, when separating items in a list, “or” or “and / or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as “only one of” or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or” as used herein shall only be interpreted as indicating exclusive alternatives (i.e., “one or the other but not both”) when preceded by terms of exclusivity, such as “either,” “one of” “only one of” or “exactly one of.” “Consisting essentially of” when used in the claims, shall have its ordinary meaning as used in the field of patent law.

[0051] As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers.

[0052] In the claims, as well as in the specification above, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” “composed of,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of” and “consisting essentially of” shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03. 12 4910-0922-0703.2

Claims

Atty. Dkt. No.142193-0122 (EM2402PCT) WHAT IS CLAIMED IS:

1. An electrochemical device comprising: an anode; a cathode; and an electrolyte; wherein the cathode comprises lithium manganese iron phosphate (LiMnxFe1-xPO4, LMFP) or sodium manganese iron phosphate (NaMnxFe1-xPO4, NMFP), or potassium manganese iron phosphate (KMnxFe1-xPO4, KMFP), and wherein the electrolyte comprises a solvent comprising N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA) or Dimethylsulfamoyl fluoride (DMSF).

2. The electrochemical device of claim 1, wherein the electrolyte comprises lithium bis(fluorosulfonyl)imide (LiFSI) or lithium hexafluorophosphate (LiPF6) substantially dissolved in the solvent.

3. The electrochemical device of claim 2, wherein the LiFSI or LiPF6 is present at a concentration of about 0.2 to about 5.0 moles of LiFSI or LiPF6 per kilogram of DMTMSA or DMSF or at a concentration of about 1.0 mole to about 2.0 moles of LiFSI or LiPF6 per kilogram of DMTMSA.

4. The electrochemical device of claim 2, wherein the LiFSI or LiPF6 is present in the electrolyte in a weight percent of from about 1% to about 30% of the electrolyte or in a weight percent of from about 5% to about 20% of the electrolyte.

5. The electrochemical device of claim 1, wherein a content of manganese (x) in LMFP, or in NMPF, or in KMFP is 0, or 1, or between 0 and 1, or from 0.4 to 0.8, or from 0.6 to 0.

8.

6. The electrochemical device of claim 1, wherein the solvent also comprises a linear carbonate, ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), or combinations thereof.

7. The electrochemical device of claim 1, wherein the electrolyte additionally comprises at least one of: fluoroethylene carbonate (FEC), 1,1,2,2-tetrafluoroethyl-2,2,3,3- 13 4910-0922-0703.2Atty. Dkt. No.142193-0122 (EM2402PCT) tetrafluoropropyl ether (TTE), prop-1-ene-1,3-sultone (PST), vinylene carbonate (VC), ethylene carbonate (EC), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), tris(trimethylsilyl)phosphite (TMSPi), Lithium Difluorophosphate (LiDFP), 1,3,2-Dioxathiolane 2,2-dioxide (DTD), or Lithium Tetrafluoro Oxalato Phosphate (LiTFOP).

8. The electrochemical device of claim 7, wherein the electrolyte comprises from 0.25 wt% to 5 wt% vinylene carbonate.

9. The electrochemical device of claim 1, wherein the electrolyte comprises no greater than 8 wt% fluoroethylene carbonate (FEC) and wherein the electrolyte comprises no greater than 15 wt% ethylene carbonate (EC) or no greater than 8 wt% ethylene carbonate (EC).

10. The electrochemical device of claim 1, wherein the electrolyte comprises no less than 1.25 wt% of 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), vinylene carbonate (VC), lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), tris(trimethylsilyl)phosphite (TMSPi), Lithium Difluorophosphate (LiDFP), 1,3,2-Dioxathiolane 2,2-dioxide (DTD), 1,3-propanesultone, Lithium Tetrafluoro Oxalato Phosphate (LiTFOP), or any combination thereof.

11. The electrochemical device of claim 1, wherein the electrolyte comprises at least 20 wt% of DMSF or DMTMSA.

12. The electrochemical device of claim 1, wherein the anode comprises hard carbon, or graphite, or silicon, or combinations thereof.

13. The electrochemical device of claim 1, wherein the cathode comprises 100 wt% of LMFP or NMFP or KMFP, or wherein the cathode comprises from 70 wt% to 30 wt% of LMFP or NMFP or KMFP.

14. The electrochemical device of claim 1, wherein the cathode also comprises from 30 wt% to 70 wt% of a compound of nickel manganese cobalt oxides (LiNixMnyCo1-x-yO2, NMC) or of lithium nickel cobalt aluminum oxides (LiNixCoyAl1-x-yO2, NCA). 14 4910-0922-0703.2Atty. Dkt. No.142193-0122 (EM2402PCT) 15. The electrochemical device of claim 1, wherein the cathode comprises metal oxides, metal sulfates, metal phosphates, metal silicates, sulfur, or combinations thereof.

16. The electrochemical device of claim 1, wherein the cathode comprises lithium cobalt oxide (LiCoO2), lithium manganese oxide (LiMn2O4), lithium nickel manganese oxide (LiNixMnyO2, LNMO), lithium iron phosphate (LiFePO4, or LFP), lithium nickel manganese cobalt oxide (LiNixMnyCo1-x-yO2or NMC), lithium nickel cobalt aluminium oxides (LiNixCoyAl1-x-yO2, NCA), or sodium vanadium phosphate Na3V2(PO4)3, or sodium nickel iron manganese oxide (NaNixFeyMn1-x-yO2), or combinations thereof.

17. The electrochemical device of claim 1 configured to operate at a temperature in a range of from -30 degrees C to 65 degrees C.

18. The electrochemical device of claim 1 configured to operate at a voltage of up to 4.7V, or up to 4.55V, or up to 4.4 V, or up to 4.3V, or up to 4.2V, or up to 3.8V, or up to 3.7V.

19. The electrochemical device of claim 1 configured to retain at least 80% capacity after 500 cycles, or after 1000 cycles, or after 2000 cycles, or after 5000 cycles.

20. A method of making an electrochemical device, wherein the method comprises providing an anode, a cathode, and an electrolyte, wherein the cathode comprises lithium manganese iron phosphate (LMFP) or sodium manganese iron phosphate (NMFP), or potassium manganese iron phosphate (KMFP), and wherein the electrolyte comprises a solvent comprising N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA) or Dimethylsulfamoyl fluoride (DMSF).

21. The method of claim 20, wherein the electrolyte comprises lithium bis(fluorosulfonyl)imide (LiFSI) or lithium hexafluorophosphate (LiPF6) substantially dissolved in the solvent.

22. A method of using an electrochemical device, wherein the method comprises providing an anode, a cathode, and an electrolyte, wherein the cathode comprises lithium manganese iron phosphate (LMFP) or sodium manganese iron phosphate (NMFP), or potassium manganese iron phosphate (KMFP), and wherein the electrolyte comprises a solvent 15 4910-0922-0703.2Atty. Dkt. No.142193-0122 (EM2402PCT) comprising N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA) or Dimethylsulfamoyl fluoride (DMSF).

23. The method of claim 22, wherein the electrolyte comprises lithium bis(fluorosulfonyl)imide (LiFSI) or lithium hexafluorophosphate (LiPF6) substantially dissolved in the solvent.

24. The method of claim 22, wherein the device operates at a temperature in a range of from - 30 degrees C to 65 degrees C.

25. The method of claim 22, wherein the device operates at a voltage of up to 4.7V, or up to 4.55V, or up to 4.4 V, or up to 4.3V, or up to 4.2V, or up to 3.8V, or up to 3.7V.

26. The method of claim 22, wherein the device retains at least 80% capacity after 500 cycles, or after 1000 cycles, or after 2000 cycles, or after 5000 cycles. 16 4910-0922-0703.2

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