Electrolyte blends for non-alkali-metal batteries

Abstract

Herein discussed is an electrochemical device comprising: an anode, a cathode, and an electrolyte; wherein the anode does not comprise pure alkali metals; and wherein the electrolyte comprises a solvent comprising at least 0.2wt% of a cyclic carbonate based on total solvent weight and at least 10wt% of N,N-dimethylsulfamoylfluoride (DMSF) or 1,1,1-trifluoro-N,N-dimethylmethanesulfonamide (DMTMSA) or mixture thereof based on total solvent weight; wherein the solvent comprises a lithium salt or a sodium salt or combination thereof substantially dissolved in the solvent at a concentration of no more than 2.5 molality, wherein molality is moles of solute divided by weight of solvent in kg; wherein the electrolyte has an ionic conductivity of no greater than 12 mS / cm at room temperature. In an embodiment, the cyclic carbonate comprises ethylene carbonate (EC), fluoroethylene carbonate (FEC), vinylene carbonate (VC), or combinations thereof.

Description

TITLE: ELECTROLYTE BLENDS FOR NON- ALKALI-METAL BATTERIES INVENTOR: GUSTAVO MARQUES HOBOLDMIN WU MATTHEW DAWSON ASSIGNEE: ELEMENTIUM MATERIALS, INC.CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No.63 / 744,142 filed January 10, 2025, entitled “ELECTROLYTE BLENDS FOR NON-ALKALI-METAL BATTERIES. " which is incorporated by reference herein in its entirety’ for all purposes.FIELD

[0002] This invention generally relates to battery' compositions. More specifically, this invention relates to electrolyte compositions for non-alkali-metal batteries.BACKGROUND

[0003] 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. Their dominance is attributed to high energy’ density, long cycle life, and relatively low self-discharge rates. Lithium-ion (Li- ion) batteries have become widely popular due to their high energy density, long cycle life, and relatively low self-discharge rate. However, they do have several disadvantages. (1) Higher Initial Cost: Li-ion batteries are more expensive to manufacture than other types of batteries like lead-acid or nickel-cadmium batteries, which can result in higher upfront costs for products that use them. (2) Risk of Overheating: Li-ion batteries can become dangerously hot if not properly110810.01316 EM2410PCTmanaged. Overheating may lead to thermal runaway, which can cause fires or even explosions. (3) Sensitivity' to Temperature: They perform poorly at very high or low temperatures, which can shorten their lifespan or reduce efficiency. (4) Degradation Over Time: Even though Li-ion batteries have a relatively long lifespan compared to other battery' types, they still degrade over time, especially if they are frequently charged and discharged. This ty pically manifests as a gradual decrease in capacity, meaning the battery' doesn't hold a charge as well as it did when new.

[0004] 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 and enhanced safety, 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 for their potential to offer a more cost- effective solution compared to LIBs. SIBs are also potentially useful in consumer electronics. 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 chargedischarge 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.210810.01316 EM2410PCTFurthermore, although sodium is abundant, the specific materials required for SIBs are still costly or difficult to source.

[0005] Clearly, there is continuing need and interest to develop improved battery systems. This disclosure discusses electrolyte blends that enhance non-alkali- metal battery performances.SUMMARY

[0006] Herein discussed is an electrochemical device comprising: an anode, a cathode, and an electrolyte; wherein the anode does not comprise pure alkali metals; and wherein the electrolyte comprises a solvent comprising at least 0.2wt% of a cyclic carbonate based on total solvent weight and at least 10wt% of N,N-dimethylsulfamoylfluoride (DMSF) or l,l,l-trifluoro-N,N- dimethylmethanesulfonamide (DMTMSA) or mixture thereof based on total solvent weight; wherein the solvent comprises a lithium salt or a sodium salt or combination thereof substantially dissolved in the solvent at a concentration of no more than 2.5 molality, wherein molality is moles of solute divided by weight of solvent in kg; wherein the electrolyte has an ionic conductivity of no greater than 12 mS / cm at room temperature. In an embodiment, the electrolyte comprises at least 30wt% of DMSF or DMTMSA or mixture thereof based on total solvent weight.

[0007] In an embodiment, the cyclic carbonate comprises ethylene carbonate (EC), fluoroethylene carbonate (FEC), vinylene carbonate (VC), or combinations thereof.

[0008] In an embodiment, the solvent is liquid at room temperature. In an embodiment, the electrolyte is liquid at 0 °C. In an embodiment, the electrolyte has a viscosity of no less than 2 cP.310810.01316 EM2410PCT

[0009] In an embodiment, the solvent also comprises one or more linear carbonates. In an embodiment, the linear carbonate comprises DMC (Dimethyl Carbonate), EMC (Ethyl Methyl Carbonate), DEC (Diethyl Carbonate), or combinations thereof. In an embodiment, the total weight percentage of linear carbonates in the solvent is no greater than 70% or in the range of from 3% to 60% or in the range of from 25% to 40%.

[0010] In an embodiment, the electrolyte also comprises one or more carboxylic esters. In an embodiment, the carboxylic ester comprises ethyl acetate (EA), methyl acetate (MA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propanoate (PP), gamma-butyrolactone (GBL), or combinations thereof.

[0011] In an embodiment, the solvent also comprises one or more sulfones (Rl- SO2-R2). In an embodiment, the sulfone comprises sulfolane, dimethyl sulfone, ethyl methyl sulfone, or combinations thereof.

[0012] In an embodiment, the electrolyte also comprises one or more ethers. In an embodiment, the ether comprises 1,2-dimethoyxethane (DME), 1,2- diethoxyethane (DEE), tetrahydrofuran (THF), methyl-tetrahydrofuran (MeTHF), dioxolane (DOL), tetrahydropyran (THP), or combinations thereof.

[0013] In an embodiment, the electrolyte comprises one or more additives, wherein each additive has a concentration of no greater than 5wt% of the electrolyte weight. In an embodiment, the additive is selected from the group consisting of vinylene carbonate (VC), LiPO2F2 (LiDFP), fluoroethylene carbonate (FEC), 1, 3, 2-di oxathiolane 2,2-dioxide (DTD), 1,3.2-dioxathiane 2,2- dioxide (TMS), 1,3-propanesultone (PS), tris(trimethylsilyl) phosphite (TMSPi), propene sultone (PES), lithium difluoro(dioxalato)phosphate (LiDFOP), lithium 410810.01316 EM2410PCTtetrafluoro(oxalato)phosphate (LiTFOP), lithium bis(oxalato)borate (LiBOB), lithium difluorooxalatoborate (LiDFOB), and combinations thereof.

[0014] In an embodiment, the salt is selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium bis(oxalato)borate (LiBOB), lithium difluorooxalatoborate (LiDFOB), lithium nitrate (LiNO3), difluoro(dioxalato)phosphate (LiDFOP), lithium tetrafluoro(oxalato)phosphate (LiTFOP), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium perchlorate (LiC104), LiPO2F2 (LiDFP), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), lithium (fluorosulfonyl)(nonafluorobutanesulfonyl)imide (LiFNFSI), lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide (LiFTFSI), sodium bis(fluorosulfonyl)imide (NaFSI), sodium hexafluorophosphate (NaPF6), sodium tetrafluoroborate (NaBF4), sodiumbis(oxalato)borate (NaBOB), sodium difluorooxalatoborate (NaDFOB), sodium nitrate (NaNO3), NaDFOP, NaTFOP, sodium bis(trifluoromethylsulfonyl)imide (NaTFSI), sodium perchlorate (NaC104), NaPO2F2 (NaDFP), sodium bis(pentafluoroethanesulfonyl)imide (NaBETI), sodium (fluorosulfonyl)(nonafluorobutanesulfonyl)imide (NaFNFSI), sodium (fluorosulfonyl)(trifluoromethanesulfonyl)imide (NaFTFSI), and combinations thereof.

[0015] In an embodiment, the solvent also comprises 1,1,2,2-Tetrafluoroethyl- 2,2,3, 3-tetrafluoropropyl ether (TTE), 1,1,2,2-Tetrafluoroethyl 2,2,2- Trifluoroethyl Ether (TFTFE). piperidine trimethysilyl amide (PIP-TMSA), trifuloroethyl ether (TFE). Trifluoroethyl methyl ether (TMF), Trifluorotoluene (PhCF3), or combinations thereof.510810.01316 EM2410PCT

[0016] In an embodiment, the anode comprises silicon, carbon, graphite, graphene, , Aluminum (Al), Tin (Sn), Bismuth (Bi), Indium (In), lithium titanium oxides, niobium oxides, titanium niobium oxides, niobium tungsten oxides, or combinations thereof, wherein optionally lithium titanium oxides comprise LiTi5O12, niobium oxides comprise Nb2O5, titanium niobium oxides comprise TiNb2O7, Ti2Nb2O9, Ti2Nbl0O29, niobium tungsten oxides comprise Nbl6W5O55, Nbl8W16O93. In an embodiment, the carbon comprises hard carbon, carbon / Al, carbon / Sn, carbon / In, carbon / graphite, carbon / Bi, or combinations thereof. In an embodiment, the graphite comprises natural graphite or artificial graphite. In an embodiment, the silicon comprises silicon oxides, metallurgical grade Si, elemental Si, silicon carbide (SiC), silicon / carbon composites (Si / C), carbon-coated Si, graphite-coated Si, graphene-coated Si, or combinations thereof. In an embodiment, silicon oxides comprise SiOx, SiO, S1O2.

[0017] In an embodiment, the cathode comprises medium nickel or medium high nickel or high nickel. In an embodiment, the cathode comprises lithium nickel manganese cobalt oxides, lithium manganese oxides, lithium nickel manganese oxides, lithium manganese iron phosphates, lithium iron phosphate (LiFePO4), lithium cobalt oxide (LiCoO2), lithium vanadium phosphates, lithium nickel oxide (LiNiO2), prussian blue analogues, prussian white analogues, or combinations thereof. In an embodiment, the lithium nickel manganese cobalt oxides comprise LiNi0.5Mn0.3Co0.202, LiNi0.6Mn0.2Co0.202, LiNi0.8Mn0.lCo0.102. LiNi0.9Mn0.05Co0.0502, LiNixMnyCol-x-y02. or combinations thereof. In an embodiment, the lithium manganese oxides comprise LiMnO2, LiMn2O4, Li2MnO2, or combinations thereof. In an embodiment, the lithium nickel 610810.01316 EM2410PCTmanganese oxides comprise LiMnl.5Ni0.5O4, Li2Mnl.5Ni0.5O4, LixMnyNizO4, or combinations thereof. In an embodiment, the lithium manganese iron phosphates comprise LiMn0.6Fe0.4PO4, LiMn0.7Fe0.3PO4, LiMn0.8Fe0.2PO4, LiMnxFe(l-x)PO4), or combinations thereof. In an embodiment, the lithium vanadium phosphates comprise Li2(VO)PO4, Li3V2(PO4)3, LiVPO4F, or combinations thereof.

[0018] In an embodiment, the device is configured to operate at a temperature in the range of from -30 degrees C to 70 degrees C. In an embodiment, the device is configured to operate at a voltage of up to 5 V, or up to 4.85 V, or up to 4.7 V, or up to 4.6 V, or up to 4.55V, or up to 4.5V, or up to 4.45 V, or up to 4.4 V, or up to 4.3V, or up to 4.2V, or up to 4 V, or up to 3.8V, or up to 3.7V, or up to 3.6 V, with a coulombic efficiency of at least 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.

[0019] Further disclosed herein are electrolyte blends as unique compositions. In an embodiment, such a composition comprises a solvent comprising from 0.2wt% to 30wt% of cyclic carbonates based on total solvent weight and at least 10wt% of sulfonamides based on total solvent weight and from 15wt% to 90wt% of linear carbonates based on total solvent weight: and lithium ions or sodium ions dissociated in the solvent, wherein the concentration of lithium ions or sodium ions dissociated in the solvent is no more than 2.5 molality, wherein molality is moles of ions divided by weight of solvent in kg; wherein the sulfonamide is selected from the group consisting of N.N-dimethylsulfamoyl fluoride (DMSF), N,N-diethylsulfamoyl fluoride (DESF). and a combination thereof: wherein the cyclic carbonates comprise at least two of the following cyclic carbonates:710810.01316 EM2410PCTethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), vinylene carbonate (VC); wherein the linear carbonates comprise at least one of the following linear carbonates: DMC (Dimethyl Carbonate), EMC (Ethyl Methyl Carbonate), DEC (Diethyl Carbonate).

[0020] In an embodiment, the composition has at least one salt substantially dissolved in the solvent, wherein the at least one salt is selected from the group consisting of lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiFSI), sodium hexafluorophosphate (NaPF6), sodium bis(fluorosulfonyl)imide (NaFSI), wherein the combined weight of LiPF6, LiFSI, NaPF6 and NaFSI in the composition is no less than 10% of the total weight of the composition.

[0021] In an embodiment, the sulfonamide has a purity of no less than 99.9% and a chloride content of no greater than 1,000 ppm, and wherein the solvent has a chloride content of no greater than 200 ppm. In an embodiment, the sulfonamide has a purity of no less than 99.9% and a chloride content of no greater than 250 ppm, and wherein the solvent has a chloride content of no greater than 25 ppm.

[0022] 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.810810.01316 EM2410PCTDETAILED DESCRIPTION

[0023] Overview. The terms "alkali ion batteries" and "alkali metal batteries refer to different types of batteries. Alkali Ion Batteries (such as LIBs and SIBs) are a type of rechargeable battery where the charge and discharge process involves the movement of alkali metal ions (such as lithium, sodium, or potassium ions) between the anode and cathode. In these batteries, an alkali metal ion (like lithium) is reversibly intercalated (inserted and extracted) into the anode and cathode materials during charge and discharge cycles. Alkali Metal Batteries (such as lithium metal batteries and sodium metal batteries) use pure alkali metals (such as lithium, sodium, or potassium) as the anode material, where the alkali metal itself is involved in the charge / discharge reactions. In these batteries, the anode will have Li metal formed during batter}7charge, and the metal is oxidized and reduced during charging and discharging, as opposed to the non-exist of alkali metal form in alkali ion batteries. The electrolyte blends of this disclosure do not apply to alkali metal batteries.

[0024] Carbonates are widely used as solvents in the electrolyte solutions of rechargeable batteries, particularly in lithium-ion (Li-ion) and other types of metal-ion batteries. Their role is critical in dissolving lithium salts (such as LiPF6) to form a conductive electrolyte that allows the movement of lithium ions between the anode and cathode during charge and discharge cycles. Despite the widespread application, carbonate electrolytes present several challenges in battery technology. (1) High voltage Instability: Carbonates can decompose at high voltages (above ~4.5 V vs Li / Li+) such as nickel-rich cathodes, leading to reduced electrolyte performance and, in some cases, safety risks like fires or explosions. (2) (2) Flammability and Safety Risks: Some carbonates, especially in 910810.01316 EM2410PCTcombination with lithium salts like LiPF6, can be flammable, which poses safety risks if the battery is damaged, punctured, or exposed to extreme conditions. (3) high temperature performance: the lithium salt LiPF6 is highly unstable at elevated temperature, causing increased electrolyte acidity, which cause the solid electrolyte interface (SEI) unstable, accelerate the electrolyte / electrode side reactions, and induce capacity decay(4) Low Temperature Performance: While carbonates offer good performance at moderate temperatures, their performance tends to degrade at low temperatures because of increased viscosity and reduced ionic conductivity. (5) gas generation: Carbonates are susceptible to side reactions, especially at high voltages or in the presence of contaminants, leading to the formation of unwanted by-products like gas. (6) fast charge performance: the SEI derived from carbonate electrolytes are organic-rich, thus has higher cell resistance, which leads to unsatisfactory fast charge performance despite having reasonably high ionic conductivity.

[0025] Electrolyte Blends. It has been unexpectedly discovered that the electrolyte blends of this disclosure enable the batteries to yield superior cycling stability and overall battery performance compared to traditional carbonate-containing electrolytes. In various embodiments, a battery contains an electrolyte having at least 0.2wt% of a cyclic carbonate based on total solvent weight and at least 10wt% of N,N-dimethylsulfamoylfluoride (DMSF, CAS No. 354-44-9) or 1,1,1- trifluoro-N,N-dimethylmethanesulfonamide (DMTMSA, CAS No. 28048-17-1) or mixture thereof based on total solvent weight; wherein the solvent comprises a lithium salt or a sodium salt or combination thereof at a concentration of no more than 2.5 molality, wherein the electrolyte has a conductivity of no greater than 12 mS / cm at room temperature.1010810.01316 EM2410PCT

[0026] In an embodiment, the electrolyte comprises at least 30wt% of DMSF or DMTMSA or mixture thereof based on total solvent weight. Although these electrolytes have lower ionic conductivity than traditional electrolytes, surprisingly the electrolyte blends of this disclosure with the specified ratios yield superior cycling stability' and overall battery' performance compared to traditional electrolytes that do not contain DMTMSA and / or DMSF within these bounds. These improvements are particularly seen with silicon-containing, carbon- containing, and / or graphite-containing anodes.

[0027] Furthermore, these electrolyte blends themselves are unique compositions.In an embodiment, such a composition comprises a solvent comprising from 0.2wt% to 30wt% of cyclic carbonates based on total solvent weight and at least 10wt% of sulfonamides based on total solvent weight and from 15wt% to 90wt% of linear carbonates based on total solvent weight; and lithium ions or sodium ions dissociated in the solvent, wherein the concentration of lithium ions or sodium ions dissociated in the solvent is no more than 2.5 molality, wherein molality is moles of ions divided by weight of solvent in kg; wherein the sulfonamide is selected from the group consisting of N,N-dimethylsulfamoyl fluoride (DMSF), N,N-diethylsulfamoyl fluoride (DESF), and a combination thereof; wherein the cyclic carbonates comprise at least two of the following cyclic carbonates: ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), vinylene carbonate (VC); wherein the linear carbonates comprise at least one of the following linear carbonates: DMC (Dimethyl Carbonate), EMC (Ethyl Methyl Carbonate), DEC (Diethyl Carbonate).

[0028] In an embodiment, the composition has at least one salt substantially dissolved in the solvent, wherein the at least one salt is selected from the group 1110810.01316 EM2410PCTconsisting of lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiFSI), sodium hexafluorophosphate (NaPF6), sodium bis(fluorosulfonyl)imide (NaFSI), wherein the combined weight of LiPF6, LiFSI, NaPF6 and NaFSI in the composition is no less than 10% of the total weight of the composition.

[0029] In an embodiment, the sulfonamide has a purity of no less than 99.9% and a chloride content of no greater than 1,000 ppm, and wherein the solvent has a chloride content of no greater than 200 ppm. In an embodiment, the sulfonamide has a purity of no less than 99.9% and a chloride content of no greater than 250 ppm, and wherein the solvent has a chloride content of no greater than 25 ppm.

[0030] Battery Compositions. In an embodiment, an electrochemical device comprises an anode, a cathode, and an electrolyte; wherein the anode does not comprise pure alkali metals; and wherein the electrolyte comprises a solvent comprising at least 0.2wt% of a cyclic carbonate based on total solvent weight and at least 10wt% of N,N-dimethylsulfamoylfluoride (DMSF) or 1,1,1 -trifluoro-N,N- dimethylmethanesulfonamide (DMTMSA) or mixture thereof based on total solvent weight; wherein the solvent comprises a lithium salt or a sodium salt or combination thereof substantially dissolved in the solvent at a concentration of no more than 2.5 molality, wherein molality is moles of solute divided by weight of solvent in kg; wherein the electrolyte has an ionic conductivity of no greater than 12 mS / cm at room temperature. In an embodiment, the electrolyte comprises at least 30wt% of DMSF or DMTMSA or mixture thereof based on total solvent weight.

[0031] In an embodiment, the cyclic carbonate comprises ethylene carbonate (EC), fluoroethylene carbonate (FEC), vinylene carbonate (VC), or combinations 1210810.01316 EM2410PCTthereof. In an embodiment, the solvent is liquid at room temperature. In an embodiment, the electrolyte is liquid at 0 °C.

[0032] In an embodiment, the solvent also comprises one or more linear carbonates. In an embodiment, the linear carbonate comprises DMC (Dimethyl Carbonate), EMC (Ethyl Methyl Carbonate), DEC (Diethyl Carbonate), or combinations thereof. In an embodiment, the total weight percentage of linear carbonates in the solvent is no greater than 70% or in the range of from 3% to 60% or in the range of from 25% to 40%.

[0033] In an embodiment, the electrolyte also comprises one or more carboxylic esters. In an embodiment, the carboxylic ester comprises ethyl acetate (EA), methyl acetate (MA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propanoate (PP), gamma-butyrolactone (GBL), or combinations thereof.

[0034] In an embodiment, the solvent also comprises one or more sulfones (Rl- SO2-R2). In an embodiment, the sulfone comprises sulfolane, dimethyl sulfone, ethyl methyl sulfone, or combinations thereof.

[0035] In an embodiment, the electrolyte also comprises one or more ethers. In an embodiment, the ether comprises 1,2-dimethoyxethane (DME), 1,2- diethoxyethane (DEE), tetrahydrofuran (THF), methyl-tetrahydrofuran (MeTHF), dioxolane (DOL), tetrahydropyran (THP), or combinations thereof.

[0036] In an embodiment, the electrolyte comprises one or more additives, wherein each additive has a concentration of no greater than 5wt% of the electrolyte weight. In an embodiment, the additive is selected from the group consisting of vinylene carbonate (VC), LiPO2F2 (LiDFP), fluoroethylene carbonate (FEC), 1, 3, 2-di oxathiolane 2,2-dioxide (DTD), 1,3.2-dioxathiane 2,2- 1310810.01316 EM2410PCTdioxide (TMS), 1,3-propanesultone (PS), tris(trimethylsilyl) phosphite (TMSPi), propene sultone (PES), lithium difluoro(dioxalato)phosphate (LiDFOP), lithium tetrafluoro(oxalato)phosphate (LiTFOP), lithium bis(oxalato)borate (LiBOB), lithium difluorooxalatoborate (LiDFOB), and combinations thereof.

[0037] In an embodiment, the electrolyte has a viscosity' of no less than 2 cP.

[0038] In an embodiment, the salt is selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), lithium bis(oxalato)borate (LiBOB), lithium difluorooxalatoborate (LiDFOB), lithium nitrate (LiNO3), difluoro(dioxalato)phosphate (LiDFOP), lithium tetrafluoro(oxalato)phosphate (LiTFOP), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium perchlorate (LiC104), LiPO2F2 (LiDFP), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), lithium (fluorosulfonyl)(nonafluorobutanesulfonyl)imide (LiFNFSI), lithium (fluorosulfonyl)(trifluoromethanesulfonyl)imide (LiFTFSI), sodium bis(fluorosulfonyl)imide (NaFSI), sodium hexafluorophosphate (NaPF6), sodium tetrafluoroborate (NaBF4), sodiumbis(oxalato)borate (NaBOB), sodium difluorooxalatoborate (NaDFOB), sodium nitrate (NaNO3), NaDFOP, NaTFOP, sodium bis(trifluoromethylsulfonyl)imide (NaTFSI), sodium perchlorate (NaC104), NaPO2F2 (NaDFP), sodium bis(pentafluoroethanesulfonyl)imide (NaBETI), sodium (fluorosulfonyl)(nonafluorobutanesulfonyl)imide (NaFNFSI), sodium (fluorosulfonyl)(trifluoromethanesulfonyl)imide (NaFTFSI), and combinations thereof.

[0039] In an embodiment, the solvent also comprises 1.1.2,2-Tetrafluoroethyl- 2.2.3.3-tetrafluoropropyl ether (TTE), 1.1.2.2-tetrafluoroethyl 2,2,2-Trifluoroethyl 1410810.01316 EM2410PCTEther (TFTFE), piperidine trimethysilyl amide (PIP-TMSA), trifuloroethyl ether (TFE), trifluoroethyl methyl ether (TMF), trifluorotoluene (PhCF3), or combinations thereof.

[0040] The electrolyte of this disclosure is suitable for use in many non-alkali- metal batteries. In various embodiments, the anode comprises silicon, carbon, graphite, prussian blue analogues, prussian white analogues, graphene, Aluminum (Al), Tin (Sn), Bismuth (Bi), Indium (In), lithium titanium oxides (comprising LiTi5O12), niobium oxides (comprising Nb2O5), titanium niobium oxides (comprising TiNb2O7, Ti2Nb2O9, Ti2Nbl0O29), niobium tungsten oxides (comprising Nbl6W5O55, Nbl8W16O93), prussian blue analogues, prussian white analogues, or combinations thereof.

[0041] In various embodiments, the carbon comprises hard carbon, carbon / Al, carbon / Sn, carbon / In, carbon / graphite, or carbon / Bi. In various embodiments, the graphite comprises natural graphite or artificial graphite. In various embodiments, the silicon comprises silicon oxides (comprising SiOx, SiO, SiO2), metallurgical grade Si, elemental Si, silicon carbide (SiC), silicon / carbon composites (Si / C), carbon-coated Si, graphite-coated Si, graphene-coated Si, or combinations thereof.

[0042] In various embodiments, the cathode comprises medium nickel or medium high nickel or high nickel. As used herein, medium nickel (Ni) means Ni contents ranging from 40% to 60%, medium high Ni means Ni contents ranging from 60% to 80%, high Ni means Ni contents higher than 80%, wherein the percentage is calculated as weight percentage in the total weight of active material in the cathode.

[0043] In various embodiments, the cathode comprises lithium nickel manganese cobalt oxides (comprising LiNi0.5Mn0.3Co0.202. LiNi0.6Mn0.2Co0.202,1510810.01316 EM2410PCTLiNiO.8MnO.lCoO.102, LiNi0.9Mn0.05Co0.0502, LiNixMnyCol-x-yO2), lithium manganese oxides (comprising LiMnO2, LiMn2O4, Li2MnO2), lithium nickel manganese oxides (comprising LiMnl.5Ni0.5O4, Li2Mnl.5Ni0.5O4, LixMnyNizO4), lithium manganese iron phosphates (comprising LiMn0.2Fe0.8PO4, LiMn0.5Fe0.5PO4, LiMn0.8Fe0.2PO4, LiMnxFe(l-x)PO4), lithium iron phosphate (LiFePO4), lithium cobalt oxide (LiCoO2), lithium vanadium phosphates (comprising Li2(VO)PO4, Li3V2(PO4)3, LiVPO4F), lithium nickel oxide (LiNiO2), prussian blue analogues, prussian white analogues, or combinations thereof.

[0044] In various embodiments, the device of this disclosure is configured to operate at a temperature in the range of from -30 degrees C to 70 degrees C. In various embodiments, the device of this disclosure is configured to operate at a voltage of up to 5V, or up to 4.85V, or up to 4.7V, or up to 4.6 V, or up to 4.55V, or up to 4.5V, or up to 4.45 V, or up to 4.4 V, or up to 4.3V, or up to 4.2V, or up to 4 V, or up to 3.8V, or up to 3.7V, or up to 3.6 V, with a coulombic efficiency of at least 99%. In various embodiments, the device of this disclosure 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.

[0045] Advantages. The compositions and properties discussed herein are contrary to conventional wisdom in many aspects yet enable better battery performance and safety.

[0046] In one aspect, conventional wisdom teaches that ethylene carbonate (EC) is highly susceptible to oxidation, especially in nickel or manganese rich cathodes. For example. EC would oxidize, deprotonate, create CO2 gas or HF or LiF, thick SEI on the cathode, and cause transition metal dissolution, high cell impedance,1610810.01316 EM2410PCTand many other failure mechanisms. In conventional thinking, whenever EC is included, the electrolyte would succumb to these failure mechanisms. However, we have unexpectedly discovered that the use of EC in combination with DMSF and / or DMTMSA in the ratios as disclosed herein prevent rapid degradation that would otherwise be expected.

[0047] In another aspect, conventionally the use of DMSF excludes carbonates in the electrolytes. But we have surprisingly found that the inclusion of cyclic carbonates significantly improves battery performance when alkali metals are not present in the anode.

[0048] In a further aspect, common understanding demands very high concentrations of salt, but we have discovered to the contrary that low concentrations of salt enable better battery performance when the anode does not contain alkali metals.

[0049] In another aspect, conventionally electrolytes require high conductivities.However, we have found that it is sufficient for the electrolyte to have a conductivity of no greater than 12 mS / cm at room temperature or no greater than 10 mS / cm at room temperature or even no greater than 9 mS / cm at room temperature.

[0050] In yet another aspect, traditional electrolytes demand low viscosities.However, we have discovered unexpectedly that even when a high viscosity cosolvent is added (e.g., EC), performance is improved. As such, the electrolyte of this disclosure has a viscosity of no less than 2 cP.

[0051] Without wishing to be limited by any theory, we believe the unexpected improvements have the following contributing factors. DMSF is a nonflammable, highly inorganic, weakly solvating solvent. Incorporating DMSF into the 1710810.01316 EM2410PCTelectrolyte suppresses the transitional metal dissolution due to the weakly solvating property7. The small molecular size and low Li solvating of DMSF lead to a quicker dissolution at the electrode / electrolyte interface compared to ty pical carbonate solvent. Thus, the SEI derived from DMSF is highly inorganic, which lowers the cell impedance. The inorganic SEI might also suppress the volume expansion in silicon anode or other high volume expansion electrodes.

[0052] However, a pure DMSF solvent has limited solubility7towards commercial LiPF6 and has non-ideal compatibility7with graphite anodes. Incorporating cosolvents (EC, EMC, DEC, PP) into DMSF-containing electrolytes as discussed herein increases electrolyte ionic conductivity7, which improves the graphite anode compatibility7as disclosed herein. In various cases, the electrolytes / compositions and methods discussed herein enable the devices to be operated in wider temperature windows.

[0053] While various inventive embodiments have been described and illustrated herein, those of ordinary7skill in the art will readily7envision a variety7of 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,1810810.01316 EM2410PCTtherefore, 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.

[0054] 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.

[0055] 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.

[0056] The indefinite articlesc‘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 / ’

[0057] 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 1910810.01316 EM2410PCTsame 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.

[0058] 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.

[0059] 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 2010810.01316 EM2410PCTspecifically 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.

[0060] 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 semiclosed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111.03.2110810.01316 EM2410PCT

Claims

CLAIMSWhat is claimed is:

1. An electrochemical device comprising: an anode, a cathode, and an electrolyte; wherein the anode does not comprise pure alkali metals; and wherein the electrolyte comprises a solvent comprising at least 0.2wt% of a cyclic carbonate based on total solvent weight and at least 10wt% of N,N-dimethylsulfamoyl fluoride (DMSF) based on total solvent weight; wherein the solvent comprises a lithium salt or a sodium salt or combination thereof substantially dissolved in the solvent at a concentration of no more than 2.5 molality, wherein molality is moles of solute divided by weight of solvent in kg; wherein the electrolyte has an ionic conductivity of no greater than 12 mS / cm at room temperature.

2. The device of claim 1, wherein the cyclic carbonate comprises ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), vinylene carbonate (VC), or combinations thereof.

3. The device of claim 1 , wherein the solvent comprises at least two of the following cyclic carbonates: ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), vinylene carbonate (VC).

4. The device of claim 1, wherein the solvent comprises no more than 30 wt% cyclic carbonates.

5. The device of claim 1, wherein the solvent is liquid at room temperature.

6. The device of claim 1, wherein the electrolyte is liquid at 0 °C.2210810.01316 EM2410PCT7. The device of claim 1, wherein the solvent also comprises one or more linear carbonates, wherein optionally the linear carbonate comprises DMC (Dimethyl Carbonate), EMC (Ethyl Methyl Carbonate), DEC (Diethyl Carbonate), or combinations thereof.

8. The device of claim 7, wherein the total weight percentage of linear carbonates in the solvent is no greater than 80% or in the range of from 15% to 60% or in the range of from 25% to 60%.

9. The device of claim 1, wherein the electrolyte also comprises one or more carboxylic esters, wherein optionally the carboxylic ester comprises ethyl acetate (EA), methyl acetate (MA), propyl acetate (PA), methyl propionate (MP), ethyl propionate (EP), propyl propanoate (PP), gamma-butyrolactone (GBL), or combinations thereof.

10. The device of claim 1, wherein the solvent also comprises one or more sulfones (Rl-SO2-R2), wherein optionally the sulfone comprises sulfolane, dimethyl sulfone, ethyl methyl sulfone, or combinations thereof.

11. The device of claim 1, wherein the electrolyte also comprises one or more ethers, wherein optionally the ether comprises 1 ,2-dimethoyxethane (DME), 1 ,2-di ethoxy ethane (DEE), tetrahydrofuran (THF), methyl-tetrahydrofuran (MeTHF), dioxolane (DOL), tetrahydropyran (THP), or combinations thereof.

12. The device of claim 1, wherein the electrolyte comprises one or more additives, wherein each additive has a concentration of no greater than 5wt% of the electrolyte weight,2310810.01316 EM2410PCTwherein optionally the additive is selected from the group consisting of vinylene carbonate (VC), vinyl ethylene carbonate (VEC), LiPO2F2 (LiDFP), fluoroethylene carbonate (FEC), 1, 3, 2-di oxathiolane 2,2-dioxide (DTD), 1,3,2-dioxathiane 2,2-dioxide (TMS), 1,3-propanesultone (PS), tris(trimethylsilyl) phosphite (TMSPi), tris(trimethylsilyl) borate (TMSB), propene sultone (PES), lithium difluoro(dioxalato)phosphate (LiDFOP), lithium tetrafluoro(oxalato)phosphate (LiTFOP), lithium bis(oxalato)borate (LiBOB), lithium difluorooxalatoborate (LiDFOB), succinonitrile (SN), adiponitrile (ADN), hexanetricarbonitrile (HTCN), and combinations thereof.

13. The device of claim 1, wherein the electrolyte has a viscosity’ of no less than 2 cP.

14. The device of claim 1, wherein at least one salt is selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), lithium hexafluorophosphate (LiPF6), lithium tetrafluoroborate (LiBF4), sodium bis(fluorosulfonyl)imide (NaFSI), sodium hexafluorophosphate (NaPF6), sodium tetrafluoroborate (NaBF4), and combinations thereof.

15. The device of claim 1, wherein the anode comprises silicon, carbon, graphite, graphene, , Aluminum (Al), Tin (Sn), Bismuth (Bi), Indium (In), lithium titanium oxides, niobium oxides, titanium niobium oxides, niobium tungsten oxides, prussian blue analogues, Prussian white analogues, or combinations thereof, wherein optionally lithium titanium oxides comprise LiTi5O12, niobium oxides comprise Nb2O5, titanium niobium oxides comprise TiNb2O7, Ti2Nb2O9, Ti2Nb 10029, niobium tungsten oxides comprise Nbl6W5O55. Nbl8W16O93, wherein optionally the carbon comprises hard carbon, carbon / Al, carbon / Sn. carbon / In, carbon / graphite, carbon / Bi, or combinations thereof, wherein optionally the graphite comprises natural graphite or artificial graphite, wherein 2410810.01316 EM2410PCToptionally the silicon comprises silicon oxides, metallurgical grade Si, elemental Si, silicon carbide (SiC), silicon / carbon composites (Si / C), carbon-coated Si, graphite-coated Si, graphene-coated Si, or combinations thereof, wherein optionally silicon oxides comprise SiOx, SiO, SiO2.

16. The device of claim 1, wherein the cathode comprises medium nickel or medium high nickel or high nickel.

17. The device of claim 1, wherein the cathode comprises lithium nickel manganese cobalt oxides, lithium manganese oxides, lithium nickel manganese oxides, lithium manganese iron phosphates, lithium iron phosphate (LiFePO4), lithium cobalt oxide (LiCoO2), lithium vanadium phosphates, lithium nickel oxide (LiNiO2), lithium manganese rich (LMR), prussian blue analogues, prussian white analogues, or combinations thereof;wherein optionally the lithium nickel manganese cobalt oxides comprise LiNi0.5Mn0.3Co0.202, LiNi0.6Mn0.2Co0.202, LiNiO.8MnO.lCoO.102, LiNi0.9Mn0.05Co0.0502, LiNixMnyCol-x-yO2, or combinations thereof;wherein optionally the lithium manganese oxides comprise LiMnO2, LiMn2O4, Li2MnO2, or combinations thereof;wherein optionally the lithium nickel manganese oxides comprise LiMnl.5Ni0.5O4, Li2Mnl.5Ni0.5O4, LixMnyNizO4, or combinations thereof;wherein optionally the lithium manganese iron phosphates comprise LiMn0.2Fe0.8PO4, LiMn0.5Fe0.5PO4, LiMn0.8Fe0.2PO4, LiMnxFe(l-x)PO4), or combinations thereof;wherein optionally the lithium vanadium phosphates comprise Li2(VO)PO4, Li3V2(PO4)3, LiVPO4F. or combinations thereof.2510810.01316 EM2410PCT18. The device of claim 1 configured to operate at a temperature in the range of from -50 degrees C to 70 degrees C.

19. The 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 4.6 V, or up to 4.55V, or up to 4.5V, or up to 4.45 V, or up to 4.4 V, or up to 4.3V, or up to 4.2V, or up to 4 V, or up to 3.8V, or up to 3.7V, or up to 3.6 V, with a coulombic efficiency of at least 99%.

20. 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.

21. A composition comprising:a solvent comprising from 0.2wt% to 30wt% of cyclic carbonates based on total solvent weight and at least 10wt% of sulfonamides based on total solvent weight and from 15wt% to 90wt% of linear carbonates based on total solvent weight; andlithium ions or sodium ions dissociated in the solvent, wherein the concentration of lithium ions or sodium ions dissociated in the solvent is no more than 2.5 molality, wherein molality is moles of ions divided by weight of solvent in kg;wherein the sulfonamide is selected from the group consisting of N,N-dimethylsulfamoyl fluoride (DMSF), N,N-diethylsulfamoyl fluoride (DESF), and a combination thereof;wherein the cyclic carbonates comprise at least two of the following cyclic carbonates: ethylene carbonate (EC), propylene carbonate (PC), fluoroethylene carbonate (FEC), vinylene carbonate (VC);2610810.01316 EM2410PCTwherein the linear carbonates comprise at least one of the following linear carbonates: DMC (Dimethyl Carbonate), EMC (Ethyl Methyl Carbonate), DEC (Diethyl Carbonate).

22. The composition of claim 21, wherein the composition has at least one salt substantially dissolved in the solvent, wherein the at least one salt is selected from the group consisting of lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiFSI), sodium hexafluorophosphate (NaPF6), sodium bis(fluorosulfonyl)imide (NaFSI), wherein the combined weight of LiPF6, LiFSI, NaPF6 and NaFSI in the composition is no less than 10% of the total weight of the composition.

23. The composition of claim 21, wherein the sulfonamide has a purity of no less than 99.9% and a chloride content of no greater than 1,000 ppm, and wherein the solvent has a chloride content of no greater than 200 ppm.

24. The composition of claim 21 , wherein the sulfonamide has a purity of no less than 99.9% and a chloride content of no greater than 250 ppm, and wherein the solvent has a chloride content of no greater than 25 ppm.2710810.01316 EM2410PCT