Improved non-lithium battery compositions

Abstract

Herein discussed is an electrochemical device. The device includes an anode, a cathode, and an electrolyte. The anode does not comprise lithium. The electrolyte includes a solvent comprising dimethyl sulfamoyl fluoride (DMSF) and a salt substantially dissolved in the solvent. The salt is selected from the group consisting of sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethylsulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPF6), and combinations thereof. Methods of making and using such devices are also disclosed.

Description

Atty. Dkt. No. 142193-0123 (EM2404PCT)IMPROVED NON-LITHIUM BATTERY COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATION

[0001] The present application claims the benefit of priority to U.S. Provisional Application No. 63 / 692,256, filed September 9, 2024, the entire content of which is incorporated herein by reference.BACKGROUND

[0002] Lithium-ion batteries are a major player in energy storage devices.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 anode does not include lithium. The electrolyte includes a solvent comprising dimethyl sulfamoyl fluoride (DMSF) and a salt substantially dissolved in the solvent. The salt is selected from the group consisting of sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethylsulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPF6), and combinations thereof.

[0004] In an embodiment, the anode includes carbon, hard carbon, graphite, silicon, sodium titanate, prussian blue analogue, tin, a salt, or a metal selected from the group consisting of barium, calcium, sodium, magnesium, copper, aluminum, and combinations thereof.

[0005] In an embodiment, the amount of DMSF in the electrolyte is no less than 80 wt%, or no less than 70 wt%, or no less than 60 wt%, or no less than 50 wt%, or no less than 40 wt%. In an embodiment, the solvent consists essentially of DMSF.

[0006] In an embodiment, the solvent also includes dimethoyxethane (DME), triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether (TEGDME), dioxolane (DOL), Tetrahydrofuran (THF), l,l,2,2-Tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), 1,1,2,2-Tetrafluoroethyl 2,2,2-Trifluoroethyl Ether (TFTFE), 1,2-di ethoxy ethane (DEE), piperidine trimethysilyl amide (PIP-TMSA), Trifuloroethyl ether(TFE), Trifluoroethyl methyl ether (TMF), N-Butyl-N- methylpyrrolidinium (Pyrl4), Trifluorotoluene (PhCF3), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), Dimethyl carbonate (DMC), ethylene carbonate (EC), Propylene carbonate (PC), ethyl acetate (EA), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB), fluoroethylene carbonate (FEC), fluorinated ethers, or combinations thereof.14911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT)

[0007] In an embodiment, the salt or the solvent includes water in the range of from 0.0001 wt% to 0.1 wt%. In an embodiment, the molality of the salt in the solvent is in the range of from 0.5 mol / kg to 3 mol / kg, wherein molality is moles of solute divided by weight of solvent in kg. In an embodiment, the salt has a molality of from 1 mol / kg to 3 mol / kg in DMSF, wherein molality is moles of solute divided by weight of DMSF in kg. In an embodiment, the salt in the electrolyte has a content in the range of from 5 wt% to 30 wt% or from 10 wt% to 20 wt%.

[0008] In an embodiment, the electrolyte does not contain more than 10 wt% carbonate solvent or more than 0.1 wt% carbonate solvent, wherein the carbonate solvent includes Ethylene carbonate, propylene carbonate, Diethyl carbonate, Dimethyl carbonate, Ethyl methyl carbonate, Fluoroethylene carbonate, or Vinylene carbonate. In an embodiment, the solvent does not contain more than 10 vol% cyclic carbonate solvent or more than 1.5 vol% cyclic carbonate solvent, wherein the cyclic carbonate solvent includes Ethylene carbonate, Propylene Carbonate (PC), Fluoroethylene carbonate, or Vinylene carbonate.

[0009] In an embodiment, the cathode includes a layered oxide, a polyanion, sodium cobalt oxide (NaCoCh), sodium chromium oxide (NaCrCh), sodium nickel iron manganese oxide (NaNixFeyMni-x-yCh), sodium nickel manganese cobalt oxide (NaNixMnyCoi-x-yCh), sodium iron phosphate (NaFePCh), sodium iron fluorophosphate (Na2FePO4F), sodium vanadium phosphate (NaVPCh), prussian blue analogue, iron based prussian white (Na2- xFeFe(CN)e), NaNixFeyMnzO2 (NFM), sodium manganese iron phosphate (Na2MnxFei-xPO4), sodium manganese rich (SMR, or manganese rich sodium), sodium manganese oxide (Na2Mn2O4), sodium cobalt oxide (Na2CoO2), or combinations thereof.

[0010] In an embodiment, the electrochemical device is configured to operate at a temperature in the range of from -30 degrees C to 65 degrees C. In an embodiment, the electrochemical device is configured to operate at a voltage of up to 5 V, or up to 4.85 V, or up to 4.7V, or up to 4.55V, or up to 4.3V, or up to 4.2V, or up to 4.0V, or up to 3.8V, or up to 3.7V, or up to 3.6V, or up to 3.5V, or up to 3.4V, or up to 3.3 V, or up to 3.2V with a coulombic efficiency of at least 99%. In an embodiment, the electrochemical device is configured to retain at least 80% capacity after 500 cycles, or after 1000 cycles, or after 2000 cycles, or after 5000 cycles at ambient temperature.

[0011] In an embodiment, the electrolyte additionally includes at least one of: fluoroethylene carbonate (FEC); l,l,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether24911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT)(TTE); 1,3-propanesultone (PS), prop-l-ene-l,3-sultone (PST); Methylene Methanedi sulfonate (MMDS), vinylene carbonate (VC); ethylene carbonate (EC); sodium bis(oxalato)borate (NaBOB); sodium tetrafluoroborate (NaBF4), sodium difluoro(oxalato)borate (NaDFOB); tris(trimethylsilyl)phosphite (TMSPi); tris(trimethylsilyl)phosphate (TMSPa); sodium difluorophosphate (NaDFP); Tris(trimethylsilyl)borate (TMSB); sodium difluoro(bisoxalato) phosphate (NaDFOP); Sodium Tetrafluoro Oxalato Phosphate (NaTFOP), sodium difluorophosphate (NaDFP); 1,3,2- Dioxathiolane 2,2-dioxide (DTD).

[0012] In an embodiment, the solvent also includes a linear carbonate, ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), or combinations thereof. In an embodiment, the electrolyte includes from 0.25 wt% to 5 wt% vinylene carbonate. 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), sodium bis(oxalato)borate (NaBOB), sodium difluoro(oxalato)borate (NaDFOB), tris(trimethylsilyl)phosphite (TMSPi), sodium difluorophosphate (NaDFP), 1,3,2- Dioxathiolane 2,2-dioxide (DTD), or any combination thereof.

[0013] In an embodiment, no component comprising more than 10 vol% of the solvent has a dielectric constant greater than 50 at 25 degrees C. In an embodiment, the specific capacity ratio of the anode to the specific capacity ratio of the cathode is from 0.9 to 2.0, or from 1.01 to 1.5, or from 1.05 to 1.2. In an embodiment, the electrochemical device has an initial coulombic efficiency of no less than 80%, or no less than 90%, or no less than 99%.

[0014] At least one aspect of the present disclosure is directed to a method of making an electrochemical device. The method includes providing an anode, a cathode, and an electrolyte. The anode does not include lithium. The electrolyte includes a solvent comprising dimethyl sulfamoyl fluoride (DMSF) and a salt substantially dissolved in the solvent. The salt is selected from the group consisting of sodium bis(fluorosulfonyl)imide (NaFSI), sodium bi s(trifluorom ethyl sulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPF6), and combinations thereof.

[0015] At least one aspect of the present disclosure is directed to a method of using an electrochemical device. The method includes providing an anode, a cathode, and an electrolyte. The anode does not include lithium. The electrolyte includes a solvent comprising dimethyl sulfamoyl fluoride (DMSF) and a salt substantially dissolved in the solvent. The salt34911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT) is selected from the group consisting of sodium bis(fluorosulfonyl)imide (NaFSI), sodium bi s(trifluorom ethyl sulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPF6), and combinations thereof.

[0016] 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

[0017] 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, certain elements of the drawing may be enlarged with respect to other elements of the drawing for purposes of illustration.

[0018] FIG. 1 illustrates the capacity retention vs. cycle number of a battery of this disclosure, according to an embodiment of this disclosure.

[0019] FIG. 2 illustrates the Coulombic efficiency vs. cycle number of a battery of this disclosure, according to an embodiment of this disclosure.DETAILED DESCRIPTION

[0020] Overview. Lithium-ion batteries are a major player in energy storage devices. However, other battery alternatives are also of interest. For example, sodium-ion batteries (SIBs) are an alternative to lithium-ion batteries (LIBs), utilizing sodium ions (Na+) for energy storage and transfer. They operate on similar principles to LIBs but use sodium-based materials in place of lithium-based ones. Sodium is more abundant and cheaper than lithium (e.g., 100 times cheaper), potentially leading to lower battery costs. SIBs have found their applications in grid energy storge. Due to their potential for lower cost, SIBs are considered suitable for large-scale energy storage systems that help stabilize power grids. They are also used in Electric Vehicles (EVs). Though less common in EVs today, SIBs are being researched for44911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT) their potential to offer a more cost-effective solution compared to LIBs. SIBs are also potentially useful in consumer electronics.

[0021] However, SIBs generally have lower energy density compared to LIBs, which affects their performance in applications requiring high energy and power density, like portable electronics and high-performance EVs. They also often suffer from shorter cycle life and lower efficiency in terms of charge-discharge cycles compared to LIBs. For applications where size and weight are critical, such as in EVs, the larger size and weight of SIBs can be a disadvantage. Furthermore, although sodium is abundant, the specific materials required for SIBs are still costly or difficult to source.

[0022] Clearly, non-lithium batteries hold promise for various applications. Therefore, there is continuing need and interest to develop improved non-lithium batteries. This disclosure discusses battery compositions that allow for the use of non-lithium anodes and that enhance battery performances.

[0023] Sodium-ion batteries (NIBs) have gained attention for their potential in large- scale energy storage due to the abundance and low cost of sodium. However, manufacturing of sodium-ion battery materials can face significant challenges that impact the scalability and safety of the technology. Key challenges may include fire safety, low energy density, and short lifespan, all of which may affect their potential for commercial applications.

[0024] (1) Fire hazard: One of the critical safety challenges in sodium-ion battery production and operation is the risk of fire associated with flammable materials used in the cell. While sodium-ion batteries are typically considered safer than lithium-ion counterparts due to sodium’s lower reactivity, they still rely on organic electrolytes, which are flammable. This may present a fire hazard during manufacturing, transport, and operation, especially when exposed to high temperatures or physical damage. Moreover, manufacturing processes for sodium-ion batteries can create dangerous conditions, such as thermal runaway. If the battery experiences internal short circuits or overcharging, it can lead to a rapid increase in temperature, which can cause the electrolyte to ignite.

[0025] (2) Sodium reactivity: While less reactive than lithium, sodium metal can still react with the electrolyte solvent, resulting in gas generation and consumption of reversible sodium ion. The sodium metal deposition could also lead to dendrite formation, penetrate the separator which poses an explosion risk. To address these safety concerns, there is ongoing research to develop non-flammable electrolytes and robust thermal management systems to54911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT) prevent overheating. Additionally, safer materials are needed for the cathode and anode to minimize fire risks, but these alternatives often come with trade-offs in terms of performance and cost.

[0026] (3) Low Energy Density: One of the primary drawbacks of sodium-ion batteries is their low energy density compared to lithium-ion batteries. Sodium ions are heavier and larger than lithium ions, the cathode and anode host materials tend to accept less sodium than lithium, which results in lower gravimetric energy density (e.g., the amount of energy stored per unit mass). The lower cell voltage further decreases the gravimetric energy density. This means sodium-ion batteries tend to have lower storage capacity, making them less suitable for high-energy applications such as electric vehicles (EVs), where size and weight are critical. The cathode materials in sodium-ion batteries, such as layered oxides or polyanionic compounds, generally exhibit lower voltage and capacity than lithium-based materials. This limits the energy density and results in shorter driving ranges or higher weight for the same amount of energy storage. To improve energy density, research is focused on finding high- performance cathode materials, such as sodium-manganese oxide or Prussian blue analogs, which can deliver higher capacities. However, the challenge remains to make these materials cost-effective and scalable for mass production.

[0027] (4) Short Lifespan and Cycle Stability: Sodium-ion batteries also suffer from shorter cycle life and lower stability compared to lithium-ion batteries. Several factors contribute to this issue: (a) Larger sodium ions cause greater mechanical stress on the electrode materials during cycling, leading to structural degradation and loss of capacity over time, (b) The solid electrolyte interphase (SEI) formed on sodium anodes is less stable than that in lithium batteries, leading to continuous electrolyte consumption and a reduction in battery life. This shorter lifespan and reduced cycle stability make sodium-ion batteries less attractive for long-term use in applications where durability is critical, such as grid energy storage or renewable energy integration.

[0028] Various efforts are attempted to overcome these issues by developing more stable electrode materials, such as carbon-based hard carbons for anodes, and improving electrolyte formulations that can form more stable SEI layers. Advanced coatings and additives are also being investigated to improve the durability and performance of the battery over many charge / discharge cycles. While sodium-ion batteries hold promise due to their low cost and the abundance of sodium, they face significant challenges that must be addressed for widespread adoption. Fire and safety concerns linked to flammable electrolytes and sodium reactivity64911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT) require innovative materials and better thermal management. The low energy density and short lifespan of sodium-ion batteries, driven by larger sodium ions and unstable SEI layers, limit their performance in high-energy applications. Ongoing research and development efforts are focused on improving material stability, enhancing energy density, and ensuring safe manufacturing processes to make sodium-ion batteries a viable option to lithium-ion technology.

[0029] Battery Compositions. It has been unexpectedly discovered that an electrolyte comprising a solvent comprising dimethyl sulfamoyl fluoride (DMSF, i.e., FSO2NC2H6) and a sodium salt substantially dissolved in the solvent allows for the use of non-lithium anode materials and mitigates many associated challenges.

[0030] Herein discussed is an electrochemical device (e.g., device). The device can include an anode, a cathode, and an electrolyte. The anode does not include lithium. The electrolyte can include a solvent including dimethyl sulfamoyl fluoride (DMSF) and a salt substantially dissolved in the solvent. The salt can be selected from the group consisting of sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethylsulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPF6), and combinations thereof.

[0031] In an embodiment, the anode includes carbon, hard carbon, graphite, silicon, sodium titanate, prussian blue analogue, a salt, or a metal selected from the group consisting of barium, calcium, sodium, magnesium, copper, aluminum, and combinations thereof.

[0032] In an embodiment, the solvent also includes dimethoyxethane (DME),Tetrahydrofuran (THF), l,l,2,2-Tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), 1,1,2,2-Tetrafluoroethyl 2,2,2-Trifluoroethyl Ether (TFTFE), 1,2-di ethoxy ethane (DEE), piperidine trimethysilyl amide (PIP-TMSA), Trifuloroethyl ether (TFE), Trifluoroethyl methyl ether (TMF), N-Butyl-N-methylpyrrolidinium (Pyrl4), Trifluorotoluene (PhCF3), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), Dimethyl carbonate (DMC), ethylene carbonate (EC), Propylene carbonate (PC), ethyl acetate (EA), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB), fluoroethylene carbonate (FEC), fluorinated ethers, or combinations thereof.

[0033] In an embodiment, the salt or the solvent includes water in the range of from0.0001 wt% to 0.1 wt%. In an embodiment, the molality of the salt in the solvent is in the range of from 0.5 mol / kg to 3 mol / kg, wherein molality is moles of solute divided by weight of74911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT) solvent in kg. In an embodiment, the salt has a molality of from 1 mol / kg to 3 mol / kg in DMSF, wherein molality is moles of solute divided by weight of DMSF in kg.

[0034] In an embodiment, the solvent does not contain more than 10 vol% carbonate solvent or more than 0.1 vol% carbonate solvent. The carbonate solvent can include Ethylene carbonate, Diethyl carbonate, Dimethyl carbonate, Ethyl methyl carbonate, Fluoroethylene carbonate, or Vinylene carbonate. In an embodiment, the salt in the electrolyte has a content in the range of from 5 wt% to 30 wt% or from 10 wt% to 20 wt%.

[0035] In an embodiment, the electrochemical device is a semi solid battery. In an embodiment, the electrolyte is a catholyte, or an anolyte, or a solid-state electrolyte.

[0036] In an embodiment, the cathode includes a layered oxide, a polyanion, sodium cobalt oxide (NaCoCh), sodium nickel manganese oxide (NaNiMnCoCh), sodium iron phosphate (Na2FePO4), sodium iron fluorophosphate (Na2FePO4F), sodium vanadium phosphate (NaVPCh), prussian blue analogue, iron based prussian white (Na2-xFeFe(CN)e) , NaNixFeyMnzO2 (NFM), sodium manganese iron phosphate (Na2MnxFei-xPO4), sodium manganese rich (SMR, or manganese rich sodium), sodium manganese oxide (FteM Ch), sodium cobalt oxide (Na2CoO2), or combinations thereof. As is known, the generic formula of a prussian blue analogue is Na2-xM[Fe(CN)6]i-ynynH2O, in which x = 0-2 and M is a single or multitransitional metal of Fe, Mn, Co, or Ni.

[0037] In an embodiment, the electrochemical device is configured to operate at a temperature in the range of from -30 degrees C to 65 degrees C. In an embodiment, the electrochemical device is configured to operate at a voltage of up to 5 V, or up to 4.85 V, or up to 4.7V, or up to 4.55V, or up to 4.3V, or up to 4.2V, or up to 3.8V, or up to 3.7V with a coulombic efficiency above 99%.

[0038] In an embodiment, the electrochemical device is configured to retain at least 80% capacity after 500 cycles, or after 1000 cycles, or after 2000 cycles, or after 5000 cycles at ambient temperature.

[0039] In an embodiment, the electrolyte additionally includes at least one of: fluoroethylene carbonate (FEC); l,l,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE); prop-l-ene-l,3-sultone (PST); vinylene carbonate (VC); ethylene carbonate (EC); lithium bis(oxalato)borate (LiBOB); lithium difluoro(oxalato)borate (LiDFOB); tris(trimethylsilyl)phosphite (TMSPi).84911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT)

[0040] In an embodiment, no component in the electrochemical device including more than 10 vol% of the solvent has a dielectric constant greater than 50 at 25 degrees C. In an embodiment, the specific capacity ratio of the anode to the specific capacity ratio of the cathode is from 0.9 to 2.0, or from 1.01 to 1.5, or from 1.05 to 1.2.

[0041] In an embodiment, the electrochemical device has an initial coulombic efficiency of no less than 80%, or no less than 90%, or no less than 99%. In an embodiment, the standard reduction potential of the solvent is no greater than 0 V, or no greater than -0.1 V, or no greater than -0.2 V; or wherein the standard oxidation potential of the solvent is no less than 5.5 V, or no less than 5.75 V, or no less than 6 V.

[0042] In an embodiment, the maximum electrostatic potential is no less than 1 eV, or no less than 1.1 eV, or no less than 1.2 eV; or wherein the minimum electrostatic potential is no less than -1.4 eV, or no less than -1.3 eV. In an embodiment, the donor number of the solvent is in the range of from 10 kcal / mol to 30 kcal / mol, or from 15 kcal / mol to 20 kcal / mol. As is known, the donor number is a measure of the ability of a solvent to solvate cations and Lewis acids.

[0043] Also disclosed herein is a method of making an electrochemical device. The method can include providing an anode, a cathode, and an electrolyte. The anode does not include lithium. The electrolyte can include a solvent including dimethylsulfamoyl fluoride (DMSF) and a salt substantially dissolved in the solvent; wherein the salt is selected from the group consisting of sodium bis(fluorosulfonyl)imide (NaFSI), sodium bi s(trifluorom ethyl sulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPF6), and combinations thereof.

[0044] Further discussed herein is a method of using an electrochemical device. The method can include providing an anode, a cathode, and an electrolyte. The anode does not include lithium. The electrolyte can include a solvent including dimethylsulfamoyl fluoride (DMSF) and a salt substantially dissolved in the solvent; wherein the salt is selected from the group consisting of sodium bis(fluorosulfonyl)imide (NaFSI), sodium bi s(trifluorom ethyl sulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPF6), and combinations thereof.

[0045] Advantages. While the use of DMSF with lithium salts in electrolyte has shown encouraging coulombic efficiency, it has been largely deemed a non-commercially viable solvent for lithium-ion battery electrolytes, especially for LiFSI based electrolytes and94911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT) especially at higher voltage. Previous research also showed that the anodic stability could be stabilized up to 4.5 V, but this required the addition of 2.5 molality of LiFSI and 0.2 molality of LiPF6, incredibly high salt concentrations, which resulted in dynamic viscosities of the electrolyte of 13.6 mPas at 20 degrees C and 11.9 mPas at 25 degrees C. This ultra-high viscosity is incompatible with conventional battery manufacturing processes, making electrolyte filling very challenging. In addition, DMSF with lithium salts issued in a very low ionic conductivity. So, while the aluminum current collector corrosion was mitigated and anodized stability realized, DMSF with lithium salts did not realize practical charging rates, experiencing significant capacity fade at just 1C charge rate. While the electrolyte at lower molality of 1.0 M LiFSI-DMSF shows decent ionic conductivities (e.g., greater than 1 mS cm1at 25 °C) with good fluidities (e.g., under 3cP at 25 °C), these benefits cannot be realized due to the anodic instability and aluminum current collector corrosion.

[0046] However remarkably, electrolytes having DMSF with as low as 1 molality NaFSI as discussed herein above exhibit anodic stability above 4V. In fact, operation above 4.5 V and even 4.7 V are allowed for DMSF with NaFSI at low molality (e.g., below 1.25), having low viscosity and sufficient ionic conductivity. This is promising to unlock high voltage operation for low-cost sodium ion batteries with reasonably fast charging capabilities.

[0047] Furthermore, DMSF can be made at low cost and much more easily than many sulfonamides that have multiple fluorinated atoms per molecule, which have to be synthesized from electrochemical fluorination, which is a very expensive and hazardous process. DMSF only has one F per molecule. This molecule is also considered far more environmentally benign as the fluorine atom can easily dissociate as fluoride. Whereas many sulfonamides having multiple fluorine atoms, bonded to carbon to form PF AS molecules, which have a chain of linked carbon and fluorine atoms. Because the carbon-fluorine bond is one of the strongest, these chemicals do not degrade easily in the environment. As such, the PFAS molecules are undergoing increasing scrutiny and regulation globally.

[0048] The electrolyte of this disclosure having DMSF with sodium salts is easier and cheaper to manufacture and more stable, which has the potential to allow for the commercial use of sodium ion batteries. The electrolyte of this disclosure having DMSF with sodium salts is very stable at high voltages, has high coulombic efficiencies, has higher energy density than conventional sodium ion batteries, has very long lifespans, and is safer and less flammable. All these properties can be key for large grid scale storage batteries, where thermal runaway104911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT) can result in catastrophic fires at the scale of large battery energy storage systems (BESS) or in the case of home BESS.EXAMPLES

[0049] 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.

[0050] Example 1. As illustrated in FIG. 1, the cycling performance of a Hard carbon / NFM cell according to an embodiment of this disclosure is tested between 1.5 V to 4 V at 1C / 1C rate. The capacity check is performed at 0.2C / 0.2C every 50 cycles. The projected lifetime is greater than 3000 cycles with 80% capacity retention. FIG. 2 illustrates the Coulombic efficiency vs. cycle number of this cell, which shows a stabilized Coulombic efficiency of greater than 99.99%.

[0051] 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 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.

[0052] 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 ordered114911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT) 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.

[0053] 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.

[0054] 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.”

[0055] 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 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.

[0056] 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.

[0057] 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 element124911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT) selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, “at least one of A and B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and / or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.

[0058] 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 2111.03.134911-9623-5875.2

Claims

Atty. Dkt. No. 142193-0123 (EM2404PCT)WHAT IS CLAIMED IS:

1. An electrochemical device comprising: an anode; a cathode; and an electrolyte; wherein the anode does not comprise lithium; wherein the electrolyte comprises a solvent comprising dimethyl sulfamoyl fluoride (DMSF) and a salt substantially dissolved in the solvent; and wherein the salt is selected from the group consisting of sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethylsulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPF6), and combinations thereof.

2. The electrochemical device of claim 1, wherein the anode comprises carbon, hard carbon, graphite, silicon, sodium titanate, prussian blue analogue, tin, a salt, or a metal selected from the group consisting of barium, calcium, sodium, magnesium, copper, aluminum, and combinations thereof.

3. The electrochemical device of claim 1, wherein an amount of DMSF in the electrolyte is no less than 80 wt%, or no less than 70 wt%, or no less than 60 wt%, or no less than 50 wt%, or no less than 40 wt%.

4. The electrochemical device of claim 1, wherein the solvent consists essentially of DMSF.

5. The electrochemical device of claim 1, wherein the solvent comprises dimethoyxethane (DME), triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether (TEGDME), dioxolane (DOL), Tetrahydrofuran (THF), l,l,2,2-Tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), 1,1,2,2-Tetrafluoroethyl 2,2,2-Trifluoroethyl Ether (TFTFE), 1,2-di ethoxy ethane (DEE), piperidine trimethysilyl amide (PIP-TMSA), Trifuloroethyl ether(TFE), Trifluoroethyl methyl ether (TMF), N-Butyl-N- methylpyrrolidinium (Pyrl4), Trifluorotoluene (PhCF3), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), Dimethyl carbonate (DMC), ethylene carbonate (EC), Propylene carbonate (PC), ethyl acetate (EA), ethyl propionate (EP), propyl propionate (PP), methyl butyrate (MB), fluoroethylene carbonate (FEC), fluorinated ethers, or combinations thereof.144911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT)6. The electrochemical device of claim 1, wherein the salt or the solvent comprises water in a range of from 0.0001 wt% to 0.1 wt%.

7. The electrochemical device of claim 1, wherein a molality of the salt in the solvent is in a range of from 0.5 mol / kg to 3 mol / kg, wherein molality is moles of solute divided by weight of solvent in kg; or wherein the salt has a molality of from 1 mol / kg to 3 mol / kg in DMSF, wherein molality is moles of solute divided by weight of DMSF in kg.

8. The electrochemical device of claim 1, wherein the electrolyte does not contain more than 10 wt% carbonate solvent or more than 0.1 wt% carbonate solvent, wherein the carbonate solvent includes Ethylene carbonate, propylene carbonate, Diethyl carbonate, Dimethyl carbonate, Ethyl methyl carbonate, Fluoroethylene carbonate, or Vinylene carbonate.

9. The electrochemical device of claim 1, wherein the solvent does not contain more than 10 vol% cyclic carbonate solvent or more than 1.5 vol% cyclic carbonate solvent, wherein the cyclic carbonate solvent includes Ethylene carbonate, Propylene Carbonate (PC), Fluoroethylene carbonate, or Vinylene carbonate.

10. The electrochemical device of claim 1, wherein the salt in the electrolyte has a content in a range of from 5 wt% to 30 wt% or from 10 wt% to 20 wt%.

11. The electrochemical device of claim 1, wherein the cathode comprises a layered oxide, a polyanion, sodium cobalt oxide (NaCoCh), sodium chromium oxide (NaCrCh), sodium nickel iron manganese oxide (NaNixFeyMni-x-yCh), sodium nickel manganese cobalt oxide (NaNixMnyCoi-x-yCh), sodium iron phosphate (NaFePCh), sodium iron fluorophosphate (Na2FePO4F), sodium vanadium phosphate (NaVPCh), prussian blue analogue, iron based Prussian white (Na2-xFeFe(CN)e), NaNixFeyMnzO2 (NFM), sodium manganese iron phosphate (Na2MnxFeiXPO4), sodium manganese rich (SMR, or manganese rich sodium), sodium manganese oxide (Na2Mn2O4), sodium cobalt oxide (Na2CoO2), or combinations thereof.

12. The electrochemical device of claim 1 configured to operate at a temperature in a range of from -30 degrees C to 65 degrees C.154911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT)13. The electrochemical device of claim 1 configured to operate at a voltage of up to 5 V, or up to 4.85V, or up to 4.7V, or up to 4.55V, or up to 4.3V, or up to 4.2V, or up to 4.0V, or up to 3.8V, or up to 3.7V, or up to 3.6 V, or up to 3.5 V, or up to 3.4 V, or up to 3.3 V, or up to 3.2 V with a coulombic efficiency of at least 99%.

14. 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 at ambient temperature.

15. The electrochemical device of claim 1, wherein the electrolyte additionally comprises at least one of: fluoroethylene carbonate (FEC); l,l,2,2-tetrafluoroethyl-2,2,3,3- tetrafluoropropyl ether (TTE); 1,3-propanesultone (PS), prop-l-ene-l,3-sultone (PST);Methylene Methanedi sulfonate (MMDS), vinylene carbonate (VC); ethylene carbonate (EC); sodium bis(oxalato)borate (NaBOB); sodium tetrafluoroborate (NaBF4), sodium difluoro(oxalato)borate (NaDFOB); tris(trimethylsilyl)phosphite (TMSPi); tris(trimethylsilyl)phosphate (TMSPa); sodium difluorophosphate (NaDFP); Tris(trimethylsilyl)borate (TMSB); sodium difluoro(bisoxalato) phosphate (NaDFOP); Sodium Tetrafluoro Oxalato Phosphate (NaTFOP), sodium difluorophosphate (NaDFP); 1,3,2-Dioxathiolane 2,2-dioxide (DTD).

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

17. The electrochemical device of claim 1, wherein the electrolyte comprises from 0.25 wt% to 5 wt% vinylene carbonate.

18. The electrochemical device of claim 1, wherein the electrolyte comprises no less than 1.25 wt% of l,l,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), vinylene carbonate (VC), sodium bis(oxalato)borate (NaBOB), sodium difluoro(oxalato)borate (NaDFOB), tris(trimethylsilyl)phosphite (TMSPi), sodium difluorophosphate (NaDFP), 1,3,2-Dioxathiolane 2,2-dioxide (DTD), or any combination thereof.164911-9623-5875.2Atty. Dkt. No. 142193-0123 (EM2404PCT)19. The electrochemical device of claim 1, wherein no component comprising more than 10 vol% of the solvent has a dielectric constant greater than 50 at 25 degrees C.

20. The electrochemical device of claim 1, wherein a specific capacity ratio of the anode to a specific capacity ratio of the cathode is from 0.9 to 2.0, or from 1.01 to 1.5, or from 1.05 to 1.2.

21. The electrochemical device of claim 1 having an initial coulombic efficiency of no less than 80%, or no less than 90%, or no less than 99%.

22. A method of making an electrochemical device, the method comprising providing an anode, a cathode, and an electrolyte; wherein the anode does not comprise lithium; wherein the electrolyte comprises a solvent comprising dimethyl sulfamoyl fluoride (DMSF) and a salt substantially dissolved in the solvent; and wherein the salt is selected from the group consisting of sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethylsulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPF6), and combinations thereof.

23. A method of using an electrochemical device, the method comprising providing an anode, a cathode, and an electrolyte; wherein the anode does not comprise lithium; wherein the electrolyte comprises a solvent comprising dimethyl sulfamoyl fluoride (DMSF) and a salt substantially dissolved in the solvent; and wherein the salt is selected from the group consisting of sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethylsulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPF6), and combinations thereof.174911-9623-5875.2

Images