Improved electrolyte compositions for batteries

Abstract

Herein discussed is an electrochemical device. The device includes an anode, a cathode, and an electrolyte. The electrolyte includes a solvent including N,N-dimethyl sulfamoyl fluoride (DMSF). The solvent includes no more than 1 wt% of N,N-dimethyl sulfamoyl chloride (DMSC). Methods of making and using such devices are also discussed herein.

Description

Atty. Dkt. No. 142193-0126 (EM2405PCT)IMPROVED ELECTROLYTE COMPOSITIONS FOR BATTERIESCROSS-REFERENCE TO RELATED APPLICATION

[0001] The present application claims the benefit of priority to U.S. Provisional Application No. 63 / 701,499, filed September 30, 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 electrolyte includes a solvent including N,N-dimethylsulfamoyl fluoride (DMSF). The solvent contains no more than 1 wt% ofN,N-dimethylsulfamoyl chloride (DMSC). In an embodiment, the DMSC content by weight in the solvent is no less than 1 ppb and no greater than 1000 ppm, or no less than 1 ppb and no greater than 100 ppm, or no less than 1 ppb and no greater than 10 ppm. In an embodiment, the electrolyte includes water by weight of no greater than 1000 ppm or no greater than 100 ppm or no greater than 20 ppm.

[0004] In an embodiment, the electrolyte includes a salt substantially dissolved in the solvent. The salt is selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium hexafluorophosphate (LiPFe), lithium difluorophosphate (LiDFP), sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethylsulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPF6), sodium difluorophosphate (NaDFP), and combinations thereof. In an embodiment, the molality of the salt in the solvent is in the range of from 0.5 mol / kg to 2.5 mol / kg or from 0.8 mol / kg to 2.0 mol / kg. Molality is moles of solute divided by weight of solvent in kg. In an embodiment, the salt does not contain more than 0.1 molality of lithium hexafluorophosphate (LiPFe), lithium difluorophosphate (LiDFP), sodium difluorophosphate (NaDFP), or sodium hexafluorophosphate (NaPF6).

[0005] In an embodiment, the DMSF content in the solvent is no less than 10 wt%. In an embodiment, the solvent includes at least one cosolvent selected from the group consisting of N-Ethyl-N-methyl sulfamoyl fluoride, dimethoyxethane (DME), Tetrahydrofuran (THF), l,l,2,2-Tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), 1,1,2,2-Tetrafluoroethyl 2,2,2-Atty. Dkt. No. 142193-0126 (EM2405PCT)Trifluoroethyl Ether (TFTFE), 1,2-di ethoxy ethane (DEE), piperidine trifluoromethanesulfonamide (PIP-TMSA), Trifluoroethyl ether(TFE), Trifluoroethyl methyl ether (TMF), N-Butyl-N- methylpyrrolidinium (Pyrl4), Trifluorotoluene (PhCF3), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), Dimethyl carbonate (DMC), propylene carbonate (PC), fluoroethylene carbonate (FEC), fluorinated ethers, methyl acetate (MA), ethyl acetate (EA), propyl acetate (PA), butyl acetate (BA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), butyl propionate (BP), methyl butyrate (MB), ethyl butyrate (EB), propyl butyrate (PB), butyl butyrate (BB), and combinations thereof. In an embodiment, the cosolvent content is no greater than 90 wt% in the solvent.

[0006] 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)b orate (LiDFOB); tris(trimethylsilyl)phosphite (TMSPi); Lithium Difluorophosphate (LiDFP); 1,3,2- Dioxathiolane 2,2-dioxide (DTD); Lithium Tetrafluoro Oxalato Phosphate (LiTFOP).

[0007] In an embodiment, the electrolyte is a catholyte, or an anolyte, or a solid-state electrolyte. 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-l-ene-l,3-sultone (PST); vinylene carbonate (VC); ethylene carbonate (EC); lithium tetrafluoroborate (LiBF4); lithium bis(oxalato)borate (LiBOB); lithium difluoro(oxalato)borate (LiDFOB); sodium tetrafluoroborate (NaBF4); sodium bis(oxalato)borate (NaBOB); sodium difluoro(oxalato)borate (NaDFOB); tris(trimethylsilyl)phosphite (TMSPi).

[0008] In an embodiment, no component having more than 10 vol% of the solvent has a dielectric constant greater than 60 at 25 degrees C. 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 lithium, barium, calcium, sodium, magnesium, copper, aluminum, and combinations thereof.

[0009] In an embodiment, the cathode includes a layered oxide, a polyanion, Lithium Nickel Manganese Cobalt Oxide (NMC), Lithium Iron Phosphate (LFP), Lithium-and-Manganese-Rich (LMR), Lithium Manganese Iron Phosphate (LMFP), LithiumAtty. Dkt. No. 142193-0126 (EM2405PCT)Cobalt Oxide (LCO), sodium cobalt oxide (NaCoO?), sodium nickel manganese oxide (NaNiMnCoO?), sodium iron phosphate (Na2FePO4), sodium iron fluorophosphate (Na2FePO4F), sodium vanadium phosphate (NaVPO4), prussian blue analogue, iron based Prussian white (Na2-xFeFe(CN)e) , 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 device is configured to operate at a temperature in the 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 4.5V, orup to 4.3V, orup to 4.2V, or up to 3.8V, or up to 3.7V with a coulombic efficiency above 99%. 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 at ambient temperature.

[0011] 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 device has an initial coulombic efficiency of no less than 80%, or no less than 90%, or no less than 99%.

[0012] 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. In an embodiment, 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.

[0013] In an embodiment, the device has a maximum electrostatic potential of no less than 1 eV, or no less than 1.1 eV, or no less than 1.2 eV. In an embodiment, the device has a minimum electrostatic potential of 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.

[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 electrolyte includes a solvent including N,N-dimethylsulfamoyl fluoride (DMSF), wherein the solvent contains no more than 1 wt% of N,N-dimethylsulfamoyl chloride (DMSC).Atty. Dkt. No. 142193-0126 (EM2405PCT)

[0015] In an embodiment, the DMSF is distilled at a reduced pressure such that its boiling point is in the range of from 30 degrees C to 70 degrees C. In an embodiment, the DMSF is synthesized by using DMSC as a reagent.

[0016] At least one aspect of the present disclosure is directed to a method of using an electrochemical device, the method including providing an anode, a cathode, and an electrolyte; wherein the electrolyte includes a solvent including N,N-dimethylsulfamoyl fluoride (DMSF), wherein the solvent contains no more than 1 wt% of N,N-dimethylsulfamoyl chloride (DMSC).

[0017] 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.DETAILED DESCRIPTION

[0018] 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 can have applications in grid energy storge. Due to their potential for lower cost, SIBs can be suitable for large-scale energy storage systems that help stabilize power grids. They can be used in Electric Vehicles (EVs). Though less common in EVs today, SIBs are being researched for their potential to offer a more cost-effective solution compared to LIBs. SIBs are also potentially useful in consumer electronics.

[0019] 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.Atty. Dkt. No. 142193-0126 (EM2405PCT)Furthermore, although sodium is abundant, the specific materials required for SIBs can be costly or difficult to source.

[0020] Clearly, lithium-ion batteries (LIBs) and non-lithium batteries hold promise for various applications. Therefore, there is continuing need and interest to develop improved battery compositions to unlock their full potential. This disclosure discusses electrolyte compositions that enhance battery performances.

[0021] Battery electrolytes are crucial components in electrochemical cells, allowing for the movement of ions between the anode and cathode, which facilitates energy storage and release. They can be liquid, solid, or gel-like, depending on the battery technology.

[0022] The earliest batteries use sulfuric acid as the electrolyte, which is relatively simple and well-understood. Nickel-Cadmium batteries used potassium hydroxide, which improved energy density and cycle life. More recently, lithium hexafluorophosphate (LiPFe) became the standard in organic solvents for lithium-based batteries, leading to high energy density and efficiency. As safety concerns rose more and more, non-flammable electrolytes have drawn much attention, which utilize components such as non-flammable solvents and additives. Among these, Solid-State Electrolytes (e.g., lithium garnets and sulfides) have gained momentum, promising improved safety and energy density.

[0023] Important factors in developing improved electrolyte compositions for batteries can include the following. (1) Safety. Flammability of liquid electrolytes poses risks, particularly in lithium-ion batteries. Thermal runaway can lead to catastrophic failures. (2) Ionic Conductivity. Achieving high ionic conductivity at room temperature is essential for efficient battery performance, especially for solid-state electrolytes. (3) Stability. Electrolyte stability against decomposition during cycling and over extended use remains a significant concern, affecting cycle life. (4) Manufacturing and Cost. Scaling up the production of advanced electrolytes is challenging and often costly.

[0024] Batery Compositions. It has been unexpectedly discovered that an electrolyte comprising a solvent comprising dimethyl sulfamoyl fluoride (DMSF, i.e., FSO2NC2H6) and containing no more than 1 wt% of dimethyl sulfamoyl chloride (DMSC) dramatically enhances battery performance. The water content of the solvent is also kept at low levels. Surprisingly, it has been discovered that the solvent system in such an electrolyte allows the use of salt content at molalities lower than conventional wisdom, while reducing current collector corrosion and allowing for high-voltage operation.Atty. Dkt. No. 142193-0126 (EM2405PCT)

[0025] Herein discussed is an electrochemical device including: an anode, a cathode, and an electrolyte. The electrolyte includes a solvent including N,N-dimethylsulfamoyl fluoride (DMSF). The solvent includes no more than 1 wt% of N,N-dimethylsulfamoyl chloride (DMSC). In an embodiment, the DMSC content by weight in the solvent is no less than 1 ppb and no greater than 1000 ppm, or no less than 1 ppb and no greater than 100 ppm, or no less than 1 ppb and no greater than 10 ppm. In an embodiment, the electrolyte includes water by weight of no greater than 5000 ppm or no greater than 1000 ppm or no greater than 100 ppm.

[0026] In an embodiment, the electrolyte includes a salt substantially dissolved in the solvent; wherein the salt is selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium hexafluorophosphate (LiPFe), sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethylsulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPFe), and combinations thereof. In an embodiment, the molality of the salt in the solvent is in the range of from 0.5 mol / kg to 2.5 mol / kg or from 0.8 mol / kg to 2.0 mol / kg, wherein molality is moles of solute divided by weight of solvent in kg. In an embodiment, the salt does not contain more than 0.1 molality of lithium hexafluorophosphate (LiPFe) or more than 0.1 molality of sodium hexafluorophosphate (NaPFe).

[0027] In an embodiment, the DMSF content in the solvent is no less than 10 wt%. In an embodiment, the solvent includes at least one cosolvent selected from the group consisting of N-Ethyl-N-methyl sulfamoyl fluoride, 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 trifluoromethanesulfonamide (PIP-TMSA), Trifluoroethyl ether(TFE), Trifluoroethyl methyl ether (TMF), N-Butyl-N- methylpyrrolidinium (Pyrl4), Trifluorotoluene (PhCF3), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), Dimethyl carbonate (DMC), fluoroethylene carbonate (FEC), fluorinated ethers, and combinations thereof. In an embodiment, the cosolvent content is no greater than 90 wt% in the solvent.

[0028] 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 lithium, barium, calcium, sodium, magnesium, copper, aluminum, and combinations thereof.Atty. Dkt. No. 142193-0126 (EM2405PCT)In an embodiment, the device is a semi solid battery. In an embodiment, the electrolyte is a catholyte, or an anolyte, or a solid-state electrolyte.

[0029] In an embodiment, the cathode includes a layered oxide, a polyanion, Lithium Nickel Manganese Cobalt Oxide (NMC), Lithium Iron Phosphate (LFP), Lithium-and-Manganese-Rich (LMR), Lithium Manganese Iron Phosphate (LMFP), Lithium Cobalt Oxide (LCO), sodium cobalt oxide (NaCoO?), sodium nickel manganese oxide (NaNiMnCoO?), sodium iron phosphate (Na2FePO4), sodium iron fluorophosphate (Na2FePO4F), sodium vanadium phosphate (NaVPO4), prussian blue analogue, iron based Prussian white (Na2-xFeFe(CN)e) , 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.

[0030] In an embodiment, the device is configured to operate at a temperature in the 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 4.5V, orup to 4.3V, orup to 4.2V, or up to 3.8V, or up to 3.7V with a coulombic efficiency above 99%. 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 at ambient temperature.

[0031] 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- 1-ene- 1,3 -sulfone (PST); vinylene carbonate (VC); ethylene carbonate (EC); lithium bis(oxalato)borate (LiBOB); lithium difluoro(oxalato)borate (LiDFOB); tris(trimethylsilyl)phosphite (TMSPi).

[0032] In an embodiment, no component having more than 10 vol% of the solvent has a dielectric constant greater than 50 at 25 degrees C. In an embodiment, no component having more than 10 vol% of the solvent has a dielectric constant greater than 60 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 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. In an embodiment, the standard oxidation potential of the solvent is no less than 5.5 V, or no less than 5.75 V, or no less thanAtty. Dkt. No. 142193-0126 (EM2405PCT)

[0033] In an embodiment, the device has a maximum electrostatic potential of no less than 1 eV, or no less than 1.1 eV, or no less than 1.2 eV. In an embodiment, the device has a minimum electrostatic potential of 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.

[0034] Also disclosed herein is a method of making an electrochemical device. The method includes providing an anode, a cathode, and an electrolyte. The electrolyte includes a solvent including N,N-dimethyl sulfamoyl fluoride (DMSF) .The solvent includes no more than 1 wt% of N,N-dimethylsulfamoyl chloride (DMSC). In an embodiment, the DMSF has been distilled at a temperature in the range of from 120 degrees C to 200 degrees C. In an embodiment, the DMSF is distilled at a reduced pressure such that its boiling point is in the range of from 30 degrees C to 70 degrees C. In an embodiment, the DMSF is synthesized by using DMSC as a reagent.

[0035] In various embodiments, DMSC is removed from DMSF by careful distillation because their boiling points are apart by less than 40 degrees C. For example, a mixture of DMSF and DMSC with a DMSC content of about 4 wt% is distilled and the resulting DMSF / DMSC mixture has a DMSC content of less than 1 wt%.

[0036] In an embodiment, a mixture of DMSF and DMSC is heated to a temperature at or above the boiling point of DMSC to depose DMSC. The decomposed components of DMSC are removed as solids or gases. In another embodiment, a mixture of DMSF and DMSC is heated with water (or any nucleophilic agent / solvent) to selectively hydrolyze DMSC to other products, which are then removed to purify DMSF.

[0037] Further discussed herein is a method of using an electrochemical device. The method includes providing an anode, a cathode, and an electrolyte. The electrolyte includes a solvent including N,N-dimethylsulfamoyl fluoride (DMSF). The solvent includes no more than 1 wt% of N,N-dimethylsulfamoyl chloride (DMSC).

[0038] 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 and especially at higher voltage because (1) It has a very poor anodic stability for aluminum current collectors above 3.75 V, above which voltage current collectors are known to rapidly corrode in DMSF and LiFSI. (2) Previous research also showed that the anodic stability could beAtty. Dkt. No. 142193-0126 (EM2405PCT) stabilized up to 4.5 V, but this required the addition of 2.5 molality of LiFSI and 0.2 molality of LiPFe, incredibly high salt concentrations, which resulted in dynamic viscosities of the electrolyte of 13.6 mPas at 20 degree C and 11.9 mPas at 25 degree C. This ultra-high viscosity is incompatible with conventional battery manufacturing processes, making electrolyte filling very challenging. (3) 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.

[0039] It has been surprisingly discovered that the low impurity level of DMSC as discussed herein is critical to ensure the proper electrolyte performance in not only lithium- based batteries but also in alternative battery compositions. There is no discussion or even realization in the literature regarding the role of DMSC content. Surprisingly, when DMSC content is kept low in DMSF, performance of batteries having DMSF-containing electrolytes dramatically improves and corrosion of aluminum current collectors is mitigated at high voltage without corrosion inhibitors and without the addition of LiPFe to passivate the current collectors.

[0040] Furthermore, the solvent system of this disclosure unexpectedly allows for the use of lower salt content. This is contrary to conventional wisdom wherein a minimum molality of 2.7 of LiFSI plus LiPFe is required to operate up to 4.5 V, see Xue, Energy Environ. Sci., 2020, 13, 212. The molarity of this disclosure is no greater than 2.5 using the present solvent system. In addition, the low water content in the electrolyte as discussed herein dramatically reduces the amount of salt required while still preventing current collector corrosion, without the need of any supplemental corrosion inhibitors. This unexpected effect allows the molality to drop below 2.5 and even below 2.0 and still allows for battery operation up to 4.5 V without corroding the current collector. These properties reduce the viscosity of the electrolyte and reduce the cost of the electrolyte because it needs substantially less salt and less expensive salt.

[0041] 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. DMSFAtty. Dkt. No. 142193-0126 (EM2405PCT) 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.

[0042] The electrolyte of this disclosure can be easier and cheaper to manufacture and more stable, which has the potential to allow for the commercial use of various batteries. The electrolyte of this disclosure is very stable at high voltages, has high coulombic efficiencies, has higher energy density than conventional batteries, has very long lifespans, and is safer and less flammable.

[0043] 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.

[0044] 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 areAtty. Dkt. No. 142193-0126 (EM2405PCT) performed in an order different than illustrated, which may include performing some acts simultaneously, even though shown as sequential acts in illustrative embodiments.

[0045] 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.

[0046] 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.”

[0047] 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.

[0048] 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.

[0049] 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 necessarilyAtty. Dkt. No. 142193-0126 (EM2405PCT) 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.

[0050] 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.

Claims

Atty. Dkt. No. 142193-0126 (EM2405PCT)WHAT IS CLAIMED IS:

1. An electrochemical device, comprising: an anode; a cathode; and an electrolyte; wherein the electrolyte comprises a solvent comprising N,N-dimethylsulfamoyl fluoride (DMSF), and wherein the solvent contains no more than 1 wt% of N,N-dimethylsulfamoyl chloride (DMSC).

2. The device of claim 1, wherein the DMSC content by weight in the solvent is no less than1 ppb and no greater than 1000 ppm, or no less than 1 ppb and no greater than 100 ppm, or no less than 1 ppb and no greater than 10 ppm.

3. The device of claim 1, wherein the electrolyte comprises water by weight of no greater than 1000 ppm or no greater than 100 ppm or no greater than 20 ppm.

4. The device of claim 1, wherein: the electrolyte comprises a salt substantially dissolved in the solvent, and the salt is selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium hexafluorophosphate (LiPFe), lithium difluorophosphate (LiDFP), sodium bis(fluorosulfonyl)imide (NaFSI), sodium bis(trifluoromethylsulfonyl)imide (NaTFSI), sodium hexafluorophosphate (NaPFe), sodium difluorophosphate (NaDFP), and combinations thereof.

5. The device of claim 4, wherein the molality of the salt in the solvent is in the range of from 0.5 mol / kg to 2.5 mol / kg or from 0.8 mol / kg to 2.0 mol / kg, wherein molality is moles of solute divided by weight of solvent in kg.

6. The device of claim 4, wherein the salt does not contain more than 0.1 molality of lithium hexafluorophosphate (LiPFe), lithium difluorophosphate (LiDFP), sodium difluorophosphate (NaDFP), or sodium hexafluorophosphate (NaPFe).Atty. Dkt. No. 142193-0126 (EM2405PCT)7. The device of claim 1, wherein the DMSF content in the solvent is no less than 10 wt%.

8. The device of claim 1, wherein the solvent comprises at least one cosolvent selected from the group consisting of N-Ethyl-N-methyl sulfamoyl fluoride, 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 trifluoromethanesulfonamide (PIP-TMSA), Trifluoroethyl ether(TFE), Trifluoroethyl methyl ether (TMF), N-Butyl-N- methylpyrrolidinium (Pyrl4), Trifluorotoluene (PhCF3), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), Dimethyl carbonate (DMC), propylene carbonate(PC), fluoroethylene carbonate (FEC), fluorinated ethers, methyl acetate (MA), ethyl acetate(EA), propyl acetate (PA), butyl acetate (BA), methyl propionate (MP), ethyl propionate (EP), propyl propionate (PP), butyl propionate (BP), methyl butyrate (MB), ethyl butyrate(EB), propyl butyrate (PB), butyl butyrate (BB), and combinations thereof.

9. The device of claim 8, wherein the cosolvent content is no greater than 90 wt% in the solvent.

10. The 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); 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); Lithium Difluorophosphate (LiDFP); 1,3,2- Dioxathiolane 2,2-dioxide (DTD); Lithium Tetrafluoro Oxalato Phosphate (LiTFOP).

11. The device of claim 1, wherein the electrolyte is a catholyte, or an anolyte, or a solid-state electrolyte.

12. The 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); prop-l-ene-l,3-sultone (PST); vinylene carbonate (VC); ethylene carbonate (EC); lithium tetrafluoroborate (LiBF4); lithium bis(oxalato)borate (LiBOB); lithium difluoro(oxalato)borate (LiDFOB); sodium tetrafluoroborate (NaBF4); sodiumAtty. Dkt. No. 142193-0126 (EM2405PCT) bis(oxalato)borate (NaBOB); sodium difluoro(oxalato)borate (NaDFOB); tris(trimethylsilyl)phosphite (TMSPi).

13. The device of claim 1, wherein no component having more than 10 vol% of the solvent has a dielectric constant greater than 60 at 25 degrees C.

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

15. The device of claim 1, wherein the cathode comprises a layered oxide, a polyanion, Lithium Nickel Manganese Cobalt Oxide (NMC), Lithium Iron Phosphate (LFP), Lithium-and-Manganese-Rich (LMR), Lithium Manganese Iron Phosphate (LMFP), Lithium Cobalt Oxide (LCO), sodium cobalt oxide (NaCoO?), sodium nickel manganese oxide (NaNiMnCoO?), sodium iron phosphate (Na2FePO4), sodium iron fluorophosphate (Na2FePO4F), sodium vanadium phosphate (NaVPO4), prussian blue analogue, iron based Prussian white (Na2-xFeFe(CN)e) , 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.

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

17. The device of claim 1 configured to operate at a voltage of up to 4.5V, or up to 4.3 V, or up to 4.2V, or up to 3.8V, or up to 3.7V with a coulombic efficiency above 99%.

18. The 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.

19. The device of claim 1, wherein 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.Atty. Dkt. No. 142193-0126 (EM2405PCT)20. The device of claim 1 having an initial coulombic efficiency of no less than 80%, or no less than 90%, or no less than 99%.

21. The device of claim 1, wherein: 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 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.

22. The device of claim 1, wherein: the device has a maximum electrostatic potential of no less than 1 eV, or no less than1.1 eV, or no less than 1.2 eV, or the device has a minimum electrostatic potential of no less than -1.4 eV, or no less than -1.3 eV.

23. The device of claim 1, wherein the donor number of the solvent is in a range of from 10 kcal / mol to 30 kcal / mol, or from 15 kcal / mol to 20 kcal / mol.

24. A method of making an electrochemical device, the method comprising: providing an anode, a cathode, and an electrolyte; wherein the electrolyte comprises a solvent comprising N,N-dimethylsulfamoyl fluoride (DMSF), and wherein the solvent contains no more than 1 wt% of N,N-dimethylsulfamoyl chloride (DMSC).

25. The method of claim 24, wherein the DMSF is distilled at a reduced pressure such that its boiling point is in a range of from 30 degrees C to 70 degrees C.

26. The method of claim 24, wherein the DMSF is synthesized by using DMSC as a reagent.

27. A method of using an electrochemical device, the method comprising: providing an anode, a cathode, and an electrolyte; wherein the electrolyte comprises a solvent comprising N,N-dimethylsulfamoyl fluoride (DMSF), andAtty. Dkt. No. 142193-0126 (EM2405PCT) wherein the solvent contains no more than 1 wt% of N,N-dimethylsulfamoyl chloride (DMSC).