Sulfonamide-based electrolytes for manganese-rich batteries

Abstract

Herein discussed is an electrochemical device comprising an anode, a cathode, and an electrolyte, wherein the cathode comprises lithium manganese iron phosphate (LiFexMn1-xPO4, LMFP), or lithium iron phosphate (LiFePO4, LFP), or Lithium Manganese Oxide (LixMnyOz, LMO), or Lithium Nickel Oxide (LNO), or Lithium Nickel Manganese Oxide (LNMO), Lithium-and-Manganese-Rich (Li1+x(NiaMnbCoc)1-xO2), (Li2MnO3)x(LiNiaMnbCocO2)(1-x), LMR), or combinations thereof, wherein the anode comprises artificial graphite or synthetic graphite or natural graphite or hard carbon, wherein the anode comprises no more than 10 wt% of silicon, wherein the anode comprises no more than 10 wt% of lithium metal, wherein the electrolyte comprises a solvent and a salt, wherein the salt is substantially dissolved in the solvent, wherein the solvent comprises a linear carbonate of no less than 30 wt% based on the electrolyte weight, and wherein the solvent comprises a sulfonamide.

Description

Title: SULFONAMIDE-BASED ELECTROLYTES FOR MANGANESE-RICH BATTERIESInventor: Min WuGustavo Marques HoboldMatthew DawsonAssignee: Elementium Materials, Inc.CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application No.63 / 790,635 filed April 17, 2025, entitled “SULFONAMIDE-BASED ELECTROLYTES FOR MANGANESE-RICH BATTERIES ' which is incorporated by reference herein in its entirety’ for all purposes.TECHNICAL FIELD

[0002] This invention generally relates to battery compositions. More specifically, this invention relates to manganese-rich batteries.BACKGROUND

[0003] LFP (Lithium Iron Phosphate) has seen widespread adoption as a cathode material in batteries. For example, LFP batteries have gained significant traction in the electric vehicle (EV) market, particularly for budget-friendly EVs. They are used by prominent manufacturers such as Tesla (for standard range versions of their vehicles), BYD, Xpeng, and others. LFP is also becoming popular in stationary’ energy storage applications due to its long cycle life, safety, and relatively low cost. It is being adopted in grid storage and renewable energy integration projects. LFP is known for its inherent safety, as the cathode material (LiFePO4) is stable and less prone to overheating or thermal runaway compared to other lithium-ion chemistries. LFP batteries also excel in cycle life, typically offering 2,000 to 5,000 cycles, which is significantly higher than many other lithium-ion chemistries like NCM (Nickel Cobalt Manganese) or NCA (Nickel Cobalt Aluminum). However, LFP’s energy density is relatively lower, around 120-160 Wh / kg, which limits its use in high-performance applications.

[0004] Mn-rich batteries, such as LMFP (Lithium Manganese Iron Phosphate) is an emerging cathode material that is a hybrid of LFP and manganese-based chemistries. LMFP offers a higher energy density while maintaining much of the safety and cost benefits of LFP.Similarly, LMR (Lithium Manganese-Rich, xLi2MnO3-(1-x) LiMO2 (0 < x < 1, M=Ni, Co, Mn, etc.)) are a promising chemistry to replace Nickel Manganese Cobalt batteries due to the much higher energy density, improved thermal stability, and lower cost. However, the biggest challenge for LMFP and LMR batteries is their short cycle life and rate capability. Clearly, there is continuing need and interest to develop compositions and devices to improve the cycle life of Mn-rich batteries and unlock their full potential in various applications.SUMMARY

[0005] Herein discussed is an electrochemical device comprising an anode, a cathode, and an electrolyte, wherein the cathode comprises lithium manganese iron phosphate (LiFexMni-XPO4. LMFP), or lithium iron phosphate (LiFePO4, LFP), or Lithium Manganese Oxide (LixMny0z, LMO), or Lithium Nickel Oxide (LNO), or Lithium Nickel Manganese Oxide (LNMO), Lithium-and-Manganese-Rich (Lii+x(NiaMnbCoc)i-xO2), (Li2MnO3)x(LiNiaMnbCocO2)( i -x), LMR), or combinations thereof, wherein the anode comprises artificial graphite or synthetic graphite or natural graphite or hard carbon, wherein the anode comprises no more than 10 wt% of silicon, wherein the anode comprises no more than 10 wt% of lithium metal, wherein the electrolyte comprises a solvent and a salt, wherein the salt is substantially dissolved in the solvent, wherein the solvent comprises a linear carbonate of no less than 30 wt% based on the electrolyte weight, and wherein the solvent comprises a sulfonamide.

[0006] In an embodiment, the electrolyte comprises a first additive comprising vinylene carbonate (VC), vinyl ethylene carbonate (VEC), vinyl ethylene sulfite (VES), 1,3-propanesultone (PS), fluoroethylene carbonate (FEC), or combinations thereof. In an embodiment, the percentage of the first additive in the electrolyte is in the range of from 0.5 wt% to 5 wt% or from 1 wt% to 3 wt%.

[0007] In an embodiment, the electrolyte comprises a second additive comprising lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), Lithium Difluorophosphate (LiDFP), Lithium difluoro(bisoxalato) phosphate (LiDFOP), Lithium tetrafluoro(bisoxalato) phosphate (LiTFOP), or combinations thereof. In an embodiment, the percentage of the second additive in the electrolyte is in the range of from 0.5 wt% to 5 wt% or from 1 wt% to 3 wt%.

[0008] In an embodiment, the anode comprises no greater than 10 wt% silicon, or no greater than 5 wt% silicon, or 0 wt% silicon. In an embodiment, the anode comprises no greater than 10 wt% lithium metal, or no greater than 5 wt% lithium metal, or 0 wt% lithium metal.

[0009] In an embodiment, the ratio of the amount of cobalt in moles in the cathode active material over the total amount of transition metals in moles in the cathode active material is no more than 0.1, or no more than 0.05, or no more than 0.02, or no more than 0.01, or zero. In an embodiment, the transition metals in the cathode active material consist of Ni, Co, Mn, and Fe. In an embodiment, the ratio of the amount of Mn in moles in the cathode active material over the total amount of transition metals in moles in the cathode active material is no less than 0.3, or no less than 0.4, or no less than 0.5, or no less than 0.6, or no less than 0.7, or no less than 0.8, or no less than 0.9, or equal to 1. In an embodiment, the transition metals in the cathode active material consist of Mn, Fe, Co, and Ni.

[0010] In an embodiment, the cathode comprises 100 wt% of LMFP. In an embodiment, the cathode comprises LMFP in the range of from 80 wt% to 20 wt%. In an embodiment, the cathode also comprises a compound of nickel manganese cobalt oxide (NMC) in the range of from 20 wt% to 80 wt%. In an embodiment, the solvent also comprises a linear ester (R1-CO2-R2), wherein the percentage of the linear ester in the solvent is no more than 20 wt%.

[0011] In an embodiment, the electrolyte comprises lithium hexafluorophosphate (LiPF6) or lithium bis(fluorosulfonyl)imide (LiFSI) substantially dissolved in the solvent. In an embodiment, the LiFSI or LiPF6 combined are present at a concentration of from about 0.2 to about 5.0 moles of LiFSI or LiPF6 per kilogram of solvent or at a concentration of from about 0.8 mole to about 2.0 moles of LiFSI or LiPF6 per kilogram of solvent. In an embodiment, the LiFSI or LiPF6 combined are present in the electrolyte at a percentage in the range of from about 1 wt% to about 30 wt% of the electrolyte or at a percentage in the range of from about 10 wt% to about 25 wt% of the electrolyte.

[0012] In an embodiment, the electrolyte comprises no more than 20 wt% ethylene carbonate (EC), or no more than 10 wt% EC, or no more than 5 wt% EC, or no more than 1 wt% EC, or 0 wt% EC. In an embodiment, the linear carbonate comprises ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), or combinations thereof. In an embodiment, the percentage of linear carbonate in the electrolyte is no more than 90 wt % or no more than 80 wt% or no more than 75 wt% based on the electrolyte weight.

[0013] In an embodiment, the sulfonamide comprises N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA), Diethylsulfamoyl fluoride (DESF), Dimethylsulfamoyl fluoride (DMSF), N-ethyl-N-methyl sulfamoyl fluoride (EMSF), N-methylsulfamoyl fluoride (MSF), bis(2-methoxyethyl)sulfamoyl fluoride (BMSF), diethylsulfamoyl fluoride (DESF), N-butyl-N. N 0, N 0-trimethylsulfamide (BTMSA), or combinations thereof. In anembodiment, the percentage of sulfonamide in the electrolyte is no less than 1 wt% or no less than 5 wt% or from 10 wt% to 30 wt%.

[0014] In an embodiment, the salt is selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiC104), lithium tetrafluoroborate (LiBF4), lithium triflouromethanesulfonate or lithium tritiate (LiTF), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), lithium tetracyanoborate (LiB(CN)4), lithium bis(oxalato)borate (LiBOB), lithium difluorooxalatoborate (LiDFOB), and combinations thereof.

[0015] Also discussed herein is an electrolyte composition comprising a cyclic carbonate ester in the range of from 0 wt% to 15 t%, a sulfonamide in the range of from 40 wt% to 5 wt%, a linear carbonate in the range of from 30 wt% to 85 wt%, a lithium salt selected from the group consisting of LiPFe, LiBF4, LiFSI, and combination thereof, wherein the percentage of the lithium salt in the electrolyte composition is in the range of from 10 wt% to 30 wt%, and a first additive selected from the group consisting of vinylene carbonate (VC), vinyl ethylene carbonate (VEC), vinyl ethylene sulfite (VES), propanesultone (PS), fluoroethylene carbonate (FEC), or combinations thereof, wherein the percentage of the first additive in the electrolyte composition is no less than 0.1 wt%, a second additive selected from the group consisting of lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), Lithium Difluorophosphate (LiDFP), Lithium difluoro(bisoxalato) phosphate (LiDFOP). Lithium tetrafluoro(bisoxalato) phosphate (LiTFOP), or combinations thereof, wherein the percentage of the second additive in the electrolyte composition is no less than 0.1 wt%.

[0016] In an embodiment, the sulfonamide comprises N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA), diethylsulfamoyl fluoride (DESF) or Dimethylsulfamoyl fluoride (DMSF), N-ethyl-N-methyl sulfamoyl fluoride (EMSF), N-methylsulfamoyl fluoride (MSF), bis(2-methoxyethyl)sulfamoyl fluoride (BMSF), diethylsulfamoyl fluoride (DESF), N-butyl-N, N 0, N 0-trimethylsulfamide (BTMSA), or combinations thereof.

[0017] In an embodiment, the composition comprises no more than 20 wt% ethylene carbonate (EC), or no more than 10 wt% EC, or no more than 5 wt% EC, or no more than 1 wt% EC, or 0 wt% EC. In an embodiment, the linear carbonate comprises ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), or combinations thereof.

[0018] In an embodiment, the composition comprises a third additive selected from the group consisting of 1,3, 2-dioxathiane-2,2-di oxide (TMS), l,3,2-dioxathiolane-2,2-dioxide (DTD),succinic anhydride (SA), prop-l-ene 1,3-sultone (PES), maleic anhydride (MA), triallyl phosphate (TAP), hexamethylene diisocyanate (HDI). methylene methanedisulfonate (MMDS), tris(trimethylsilyl)phosphite (TMSPi), tris(trimethylsilyl)phosphate (TMSPa), 1,3-propanesultone, ethylene sulfite (ES), tris(trimethylsilyl) Borate (TMSB), trimethyl borate (TMO), a nitrile, and combinations thereof. In an embodiment, the percentage of the third additive in the electrolyte composition is in the range of from 0.1 wt% to 5 wt%. In an embodiment, the nitrile comprises Succinonitrile (SN), Adiponitrile (ADN), 1,3,6-Hexanetricarbonitrile (HTCN), or combinations thereof.

[0019] 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

[0020] 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.

[0021] FIG. 1 compares the cycling performance of artificial graphite (AG)||LMFP cells using the electrolyte of this disclosure with the cycling performance of cells using market leader electrolyte, according to an embodiment of this disclosure.

[0022] FIG. 2 compares the Direct Current Internal Resistance (DCIR) growth during cy cling of artificial graphite (AG)||LMFP cells using the electrolyte of this disclosure with DCIR growth during cycling of cells using market leader electrolyte, according to an embodiment of this disclosure.DETAILED DESCRIPTION

[0023] Overview. LFP batteries use lithium iron phosphate (LiFePO4) as the cathode material. The anode typically consists of graphite, including as natural graphite, syntheticgraphite, artificial graphite, or combinations thereof. LMFP batteries are similar to LFP batteries but have manganese (LiFeixMnxPC>4, where x indicates the proportion of manganese) incorporated into the cathode material alongside iron and phosphate. Ethylene carbonate (EC) has been traditionally used in the electrolyte for LFP and LMFP batteries. EC has a high ionic conductivity and has the tendency to dissolve and wash away the manganese in the cathode, which contributes to the shorter cycle life of LMFP batteries compared to LFP batteries.

[0024] We have unexpectedly discovered that electrolytes that do not contain EC and that use solvents of low dielectric constant are effective for Graphite / LMFP batteries, provided that certain additives are used to passivate graphite and LMFP. More specifically, we have unexpectedly discovered that electrolytes containing N. N-dimethyltrifluoromethane-sulfonamide (DMTMSA, CAS No. 28048-17-1) orN, N-dimethylsulfamoyl fluoride (DMSF, CAS No. 354-44-9) or other low dielectric constant sulfonamides are effective in preventing transition metal dissolution, thus enable high performance cycling of LMFP batteries. In addition, the manganese-rich batteries of this disclosure are able to be operated at higher voltages, such as up to 4.3 V compared to the traditional 3.6 V. When the discharge / charge rate is 1C, these batteries have a life of 2000 cycles or more.

[0025] Electrolyte Compositions. The unexpectedly discovered electrolyte composition has many variations and embodiments. In an embodiment, an electrolyte composition comprises a cyclic carbonate ester in the range of from 0 wt% to 15 wt%, a sulfonamide in the range of from 40 wt% to 5 wt%, a linear carbonate in the range of from 30 wt% to 85 wt%, a lithium salt selected from the group consisting of LiPF6, LiFSI, and combination thereof, wherein the percentage of the lithium salt in the electrolyte composition is in the range of from 10 wt% to 30 wt%, and an additive selected from the group consisting of vinylene carbonate (VC); 1,3,2-dioxathiane-2,2-dioxide (IMS); l,3,2-dioxathiolane-2,2-dioxide (DTD); prop-l-ene 1,3-sultone (PES); succinic anhydride (SA); maleic anhydride (MA); trially 1 phosphate (TAP); hexamethylene diisocyanate (HDI); methylene methanedisulfonate (MMDS), lithium bis(oxalato)borate (LiBOB); lithium difluoro(oxalato)borate (LiDFOB); Lithium Difluorophosphate (LiDFP); tris(trimethylsilyl)phosphite (TMSPi), fluoroethylene carbonate (FEC); tris(trimethylsilyl)phosphate (TMSPa): 1,3-propanesultone, ethylene sulfite (ES), tris( trimethylsilyl) Borate (TMSB), trimethyl borate (TMO), and the nitrile additives such as Succinonitrile ( SN), Adiponitrile (ADN), 1,3,6-Hexanetricarbonitrile (HTCN), and combinations thereof, wherein the percentage of the additive in the electrolyte composition is in the range of from 0.1 wt% to 5 wt%.

[0026] In an embodiment, the sulfonamide comprises N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA), Diethylsulfamoyl fluoride (DESF), Dimethylsulfamoyl fluoride (DMSF), N-ethyl-N-methyl sulfamoyl fluoride (EMSF), N-methylsulfamoyl fluoride (MSF), bis(2-methoxyethyl)sulfamoyl fluoride (BMSF), diethylsulfamoyl fluoride (DESF), N-butyl-N, N 0, N O-trimethylsulfamide (BTMSA), or combinations thereof.

[0027] In an embodiment, the electrolyte composition comprises no more than 20 wt% ethylene carbonate, or no more than 10 wt% ethylene carbonate (EC), or no more than 5 wt% EC, or no more than 1 wt% EC, or 0 wt% EC. In an embodiment, the linear carbonate comprises ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), or combinations thereof.

[0028] In an embodiment, an electrolyte composition comprises a cyclic carbonate ester in the range of from 0 wt% to 15 wt%, a sulfonamide in the range of from 40 wt% to 5 wt%, a linear carbonate in the range of from 30 wt% to 85 wt%, a lithium salt selected from the group consisting of LiPF6, LiBF4, LiFSI, and combination thereof, wherein the percentage of the lithium salt in the electrolyte composition is in the range of from 10 wt% to 30 wt%, and a first additive selected from the group consisting of vinylene carbonate (VC), vinyl ethylene carbonate (VEC), vinyl ethylene sulfite (VES), propanesultone (PS), fluoroethylene carbonate (FEC), or combinations thereof, wherein the percentage of the first additive in the electrolyte composition is no less than 0.1 wt%, a second additive selected from the group consisting of lithium bis(oxalato)borate (LiBOB). lithium difluoro(oxalato)borate (LiDFOB), Lithium Difluorophosphate (LiDFP), Lithium difluoro(bisoxalato) phosphate (LiDFOP), Lithium tetrafluoro(bisoxalato) phosphate (LiTFOP), or combinations thereof, wherein the percentage of the second additive in the electrolyte composition is no less than 0.1 wt%.

[0029] In an embodiment, the sulfonamide comprises N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA), diethylsulfamoyl fluoride (DESF) or Dimethylsulfamoyl fluoride (DMSF), N-ethyl-N-methyl sulfamoyl fluoride (EMSF), N-methylsulfamoyl fluoride (MSF), bis(2-methoxyethyl)sulfamoyl fluoride (BMSF), diethylsulfamoyl fluoride (DESF), N-butyl-N, N 0, N O-trimethylsulfamide (BTMSA), or combinations thereof.

[0030] In an embodiment, the composition comprises no more than 20 wt% ethylene carbonate (EC), or no more than 10 wt% EC, or no more than 5 wt% EC, or no more than 1 wt% EC, or 0 wt% EC. In an embodiment, the linear carbonate comprises ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), or combinations thereof.

[0031] In an embodiment, the composition comprises a third additive selected from the group consisting of 1,3,2-dioxathiane-2,2-dioxide (TMS), 1,3,2-dioxathiolane-2,2-dioxide (DTD), succinic anhydride (SA), prop-l-ene 1,3-sultone (PES), maleic anhydride (MA), triallyl phosphate (TAP), hexamethylene diisocyanate (HDI), methylene methanedisulfonate (MMDS), tris(trimethylsilyl)phosphite (TMSPi), tris(trimethylsilyl)phosphate (TMSPa), 1,3-propanesultone, ethylene sulfite (ES), tris(trimethylsilyl) Borate (TMSB), trimethyl borate (TMO), a nitrile, and combinations thereof. In an embodiment, the percentage of the third additive in the electrolyte composition is in the range of from 0.1 wt% to 5 wt%. In an embodiment, the nitrile comprises Succinonitrile (SN), Adiponitrile (ADN), 1,3,6-Hexanetricarbonitrile (HTCN), or combinations thereof.

[0032] Battery Compositions. Herein discussed is an electrochemical device comprising an anode, a cathode, and an electrolyte, wherein the cathode comprises lithium manganese iron phosphate (LiFexMni xPCh, LMFP), or lithium iron phosphate (LiFePO4, LFP), or Lithium Manganese Oxide (LixMnyOz, LMO), or Lithium Nickel Oxide (LNO), or Lithium Nickel Manganese Oxide (LNMO), Lithium-and-Manganese-Rich(Lii+x(NiaMnbCoc)i-xO2), (Li2MnO3)x(LiNiaMnbCocO2)d-X), LMR), or combinations thereof, wherein the anode comprises artificial graphite or synthetic graphite or natural graphite or hard carbon, wherein the anode comprises no more than 10 wt% of silicon, wherein the anode comprises no more than 10 wt% of lithium metal, wherein the electrolyte comprises a solvent and a salt, wherein the salt is substantially dissolved in the solvent, wherein the solvent comprises a linear carbonate of no less than 30 wt% based on the electrolyte weight, and wherein the solvent comprises a sulfonamide.

[0033] In an embodiment, the electrolyte comprises a first additive comprising vinylene carbonate (VC), vinyl ethylene carbonate (VEC), vinyl ethylene sulfite (VES), 1,3-propanesultone (PS), fluoroethylene carbonate (FEC), or combinations thereof. In an embodiment, the percentage of the first additive in the electrolyte is in the range of from 0.5 wt% to 5 wt% or from 1 wt% to 3 wt%.

[0034] In an embodiment, the electrolyte comprises a second additive comprising lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), Lithium Difluorophosphate (LiDFP), Lithium difluoro(bisoxalato) phosphate (LiDFOP), Lithium tetrafluoro(bisoxalato) phosphate (LiTFOP), or combinations thereof. In an embodiment, the percentage of the second additive in the electrolyte is in the range of from 0.5 wt% to 5 wt% or from 1 wt% to 3 wt%.

[0035] In an embodiment, the anode comprises no greater than 10 wt% silicon, or no greater than 5 wt% silicon, or 0 wt% silicon. In an embodiment, the anode comprises no greater than 10 wt% lithium metal, or no greater than 5 wt% lithium metal, or 0 wt% lithium metal.

[0036] In an embodiment, the ratio of the amount of cobalt in moles in the cathode active material over the total amount of transition metals in moles in the cathode active material is no more than 0.1, or no more than 0.05, or no more than 0.02, or no more than 0.01, or zero. In an embodiment, the transition metals in the cathode active material consist of Ni, Co, Mn, and Fe. In an embodiment, the ratio of the amount of Mn in moles in the cathode active material over the total amount of transition metals in moles in the cathode active material is no less than 0.3, or no less than 0.4, or no less than 0.5, or no less than 0.6, or no less than 0.7, or no less than 0.8, or no less than 0.9, or equal to 1. In an embodiment, the transition metals in the cathode active material consist of Mn, Fe, Co, and Ni.

[0037] In an embodiment, the cathode comprises 100 wt% of LMFP. In an embodiment, the cathode comprises LMFP in the range of from 80 wt% to 20 wt%. In an embodiment, the cathode also comprises a compound of nickel manganese cobalt oxide (NMC) in the range of from 20 wt% to 80 wt%. In an embodiment, the solvent also comprises a linear ester (Rl-CO2-R2), wherein the percentage of the linear ester in the solvent is no more than 20 wt%.

[0038] In an embodiment, the electrolyte comprises lithium hexafluorophosphate (LiPF6) or lithium bis(fluorosulfonyl)imide (LiFSI) substantially dissolved in the solvent. In an embodiment, the LiFSI or LiPF6 combined are present at a concentration of from about 0.2 to about 5.0 moles of LiFSI or LiPF6 per kilogram of solvent or at a concentration of from about 0.8 mole to about 2.0 moles of LiFSI or LiPF6 per kilogram of solvent. In an embodiment, the LiFSI or LiPF6 combined are present in the electrolyte at a percentage in the range of from about 1 wt% to about 30 wt% of the electrolyte or at a percentage in the range of from about 10 wt% to about 25 wt% of the electrolyte.

[0039] In an embodiment, the electrolyte comprises no more than 20 wt% ethylene carbonate (EC), or no more than 10 wt% EC, or no more than 5 wt% EC, or no more than 1 wt% EC, or 0 wt% EC. In an embodiment, the linear carbonate comprises ethyl methyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), or combinations thereof. In an embodiment, the percentage of linear carbonate in the electrolyte is no more than 90 wt% or no more than 80 wt% or no more than 75 wt% based on the electrolyte weight.

[0040] In an embodiment, the sulfonamide comprises N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA), Diethylsulfamoyl fluoride (DESF), Dimethylsulfamoyl fluoride (DMSF), N-ethyl-N-methyl sulfamoyl fluoride (EMSF), N-methylsulfamoyl fluoride(MSF), bis(2-methoxyethyl)sulfamoyl fluoride (BMSF), diethylsulfamoyl fluoride (DESF), N-butyl-N, N 0, N O-trimethylsulfamide (BTMSA), or combinations thereof. In an embodiment, the percentage of sulfonamide in the electrolyte is no less than 1 wt% or no less than 5 wt% or from 10 wt% to 30 wt%.

[0041] In an embodiment, the salt is selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiC104), lithium tetrafluoroborate (LiBF4), lithium triflouromethanesulfonate or lithium triflate (LiTF), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), lithium tetracyanoborate (LiB(CN)4), lithium bis(oxalato)borate (LiBOB), lithium difluorooxalatoborate (LiDFOB), and combinations thereof.

[0042] According to this disclosure, in a further embodiment, an electrochemical device comprises an anode, a cathode, and an electrolyte, wherein the cathode comprises lithium manganese iron phosphate (LMFP), or lithium iron phosphate (LFP), or Lithium Manganese Oxide (LMO), or Lithium Nickel Oxide (LNO). or Lithium Nickel Manganese Oxide (LNMO), wherein the anode comprises artificial graphite or synthetic graphite or hard carbon, wherein the anode comprise no more than 10 \\1% of silicon, wherein the anode comprises no more than 10 wt% of lithium metal, wherein the electrolyte comprises a solvent and a salt, wherein the salt is substantially dissolved in the solvent, wherein the solvent comprises a linear carbonate of no less than 40 wt% based on the electrolyte weight, and wherein the solvent comprises a sulfonamide.

[0043] In an embodiment, the electrolyte comprises an additive, wherein the additive comprises vinylene carbonate (VC); 1,3,2-dioxathiane-2,2-dioxide (TMS); 1,3,2-dioxathiolane-2,2-dioxide (DTD); prop-1-ene 1,3-sultone (PES); succinic anhydride (SA); maleic anhydride (MA); triallyl phosphate (TAP); hexamethylene diisocyanate (HDI); methylene methanedisulfonate (MMDS), lithium bis(oxalato)borate (LiBOB); lithium difluoro(oxalato)borate (LiDFOB); Lithium Difluorophosphate (LiDFP); tris(trimethylsilyl)phosphite (TMSPi), fluoroethylene carbonate (FEC); tris(trimethylsilyl)phosphate (TMSPa); 1,3-propanesultone, ethylene sulfite (ES), tris(trimethylsilyl) Borate (TMSB), trimethyl borate (TMO), and the nitrile additives such as Succinonitrile (SN), Adiponitrile (ADN), 1,3,6-Hexanetricarbonitrile (HTCN), or combinations thereof. In an embodiment, the percentage of the additive in the electrolyte is in the range of from 0.5 wt% to 5 wt% or from 1 wt% to 3 wt%.

[0044] In an embodiment, the sulfonamide comprises N, N-dimethyltrifluoromethane-sulfonamide (DMTMSA), Diethylsulfamoyl fluoride (DESF), Dimethylsulfamoyl fluoride (DMSF), N-ethyl-N-methyl sulfamoyl fluoride (EMSF), N-methylsulfamoyl fluoride (MSF), bis(2-methoxyethyl)sulfamoyl fluoride (BMSF), diethylsulfamoyl fluoride (DESF), N-butyl-N, N 0, N O-trimethylsulfamide (BTMSA), or combinations thereof. In an embodiment, the percentage of sulfonamide in the electrolyte is no less than 1 wt% or no less than 5 wt% or from 10 wt% to 30 wt%. In an embodiment, the device is configured to be operated at up to 4.3 V for 2000 cycles or more at a charge / discharge rate of 1C.

[0045] In an embodiment, the anode comprises no greater than 10 wt% silicon, or no greater than 5 wt% silicon, or 0 wt% silicon. In an embodiment, the cathode comprises 100 wt% of LMFP. or wherein the cathode comprises LMFP in the range of from 80 wt% to 20 wt%. In an embodiment, the cathode also comprises a compound of nickel manganese cobalt oxide (NMC) in the range of from 20 wt% to 80 wt%.

[0046] In an embodiment, the electrolyte comprises lithium hexafluorophosphate (LiPF6) or lithium bis(fluorosulfonyl)imide (LiFSI) substantially dissolved in the solvent. In an embodiment, the LiFSI or LiPF6 is present at a concentration of from about 0.2 to about 5.0 moles of LiFSI or LiPF6 per kilogram of solvent or at a concentration of from about 0.8 mole to about 2.0 moles of LiFSI or LiPF6 per kilogram of solvent. In an embodiment, the LiFSI or LiPF6 is present in the electrolyte in a percentage of from about 1 wt% to about 30 wt% of the electrolyte or in a percentage of from about 10 wt% to about 25 wt% of the electrolyte.

[0047] In an embodiment, the electrolyte comprises no more than 20 wt% ethylene carbonate (EC), or no more than 10 wt% ethylene carbonate (EC), or no more than 5 wt% EC, or no more than 1 wt% EC, or 0 wt% EC. In an embodiment, the linear carbonate comprises ethyl methyl carbonate (EMC), dimethyl carbonate (DMC). diethyl carbonate (DEC), or combinations thereof. In an embodiment, the percentage of linear carbonate in the electrolyte is no more than 90 \\ t% or no more than 80 wt% or no more than 75 wt% based on the electrolyte weight.

[0048] In an embodiment, the solvent also comprises a linear ester, wherein the percentage of the linear ester in the solvent is no more than 20 wt%. In an embodiment, the solvent has a dielectric constant of no greater than 10. In an embodiment, the salt is selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), lithium triflouromethanesulfonate or lithium triflate (LiTF), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), lithiumtetracyanoborate (LiB(CN)4), lithium bis(oxalato)borate (LiBOB), lithium difluorooxalatoborate (LiDFOB), and combinations thereof.

[0049] Advantages. The electrolyte formulation of this disclosure unlocks ultra long cycle life in batteries with manganese-rich cathode, as well as enhanced rate capability. For example, we have seen the potential to increase the cycle life of LMFP based batteries twofold over state-of-the-art commercial electrolytes, reaching 3000 cycles at 1 C charge and discharge rates when operated at 4.3 V. The market implications of this are groundbreaking. Today’s most commonly used cathode material for lithium-ion batteries is lithium iron phosphate (LFP). LMFP batteries provide much higher energy density, resulting in lighter weight, more compact and potentially lower cost batteries. However, LMFP batteries have historically struggled with short cycle life due to transition metal dissolution from the highly salivating electrolytes that are conventionally used.

[0050] The electrolyte of this disclosure utilizes a solvent with low dielectric constant and low salt solubility, and thus low ionic conductivity, which is the exact opposite of conventional targets of high solubility and high ionic conductivity electrolytes. The intrinsically low solubility of this electrolyte mitigates transition metal dissolution, enabling LMFP batteries to achieve substantially longer cycle life. Moreover, the electrolyte as disclosed herein forms very thin, stable, and more inorganic and conductive solid electrolyte interfaces in the anode, which promotes lower overall cell impedance, and therefore higher rate capability, which conventional LMFP batteries could not attain to.

[0051] Example. This example demonstrates the cycling stability of artificial graphite (AG)||LMFP batteries using an electrolyte of this disclosure compared to batteries using a market-leading carbonate electrolyte.

[0052] As illustrated in Fig. 1. the control battery uses a carbonate-based electrolyte containing multiple additives, including but not limited to VC and LiDFP. In contrast, the battery described in this disclosure utilizes a sulfonamide solvent along with other low dielectric constant solvents. The capacity retention versus cycle number data shows that the sulfonamide-based electrolyte significantly outperforms the carbonate-based system. While the leading carbonate electrolyte projects approximately 1800 cycles at 80% capacity’ retention, the sulfonamide electrolyte exceeds 3000 cycles at the same retention level.

[0053] Fig. 2 compares cell impedance growth between the two electrolytes. The battery with the sulfonamide electrolyte exhibits less than 5% impedance growth, whereas the carbonate-based battery shows approximately 30% growth. This pronounced difference is likely due tothe sulfonamide electrolyte's ability to suppress Mn3+dissolution, thereby enhancing overall cycling stability.

[0054] 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.

[0055] 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.

[0056] 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.

[0057] 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.”

[0058] 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 areconjunctively 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 anon-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.

[0059] 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.

[0060] As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, 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.

[0061] 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

CLAIMSWhat is claimed is:

1. An electrochemical device comprising:an anode, a cathode, and an electrolyte,wherein the cathode comprises lithium manganese iron phosphate (LiFexMn1-xPO4, LMFP), or lithium iron phosphate (LiFePO4, LFP), or Lithium Manganese Oxide (LixMnyOz, LMO), or Lithium Nickel Oxide (LNO), or Lithium Nickel Manganese Oxide (LNMO), Lithium-and-Manganese-Rich (Li1+x(NiaMnbCoc)1-xO2), (Li2MnO3)x(LiNiaMnbCocO2)(1-x), LMR), or combinations thereof,wherein the anode comprises artificial graphite or synthetic graphite or natural graphite or hard carbon, wherein the anode comprises no more than 10 wt% of silicon, wherein the anode comprises no more than 10 wt% of lithium metal,wherein the electrolyte comprises a solvent and a salt, wherein the salt is substantially dissolved in the solvent,wherein the solvent comprises a linear carbonate of no less than 30 wt% based on the electrolyte weight,and wherein the solvent comprises a sulfonamide.

2. The device of claim 1, wherein the electrolyte comprises a first additive comprising vinylene carbonate (VC), vinyl ethylene carbonate (VEC), vinyl ethylene sulfite (VES), 1,3-propanesultone (PS), fluoroethylene carbonate (FEC). or combinations thereof.

3. The device of claim 2, wherein the percentage of the first additive in the electrolyte is in the range of from 0.5 wt% to 5 wt% or from 1 wt% to 3 wt%.

4. The device of claim 1, wherein the electrolyte comprises a second additive comprising lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), Lithium Difluorophosphate (LiDFP), Lithium difluoro(bisoxalato) phosphate (LiDFOP), Lithium tetrafluoro(bisoxalato) phosphate (LiTFOP), or combinations thereof.

5. The device of claim 4, wherein the percentage of the second additive in the electrolyte is in the range of from 0.5 wt% to 5 wt% or from 1 wt% to 3 wt%.

6. The device of claim 1, wherein the anode comprises no greater than 10 wt% silicon, or no greater than 5 wt% silicon, or 0 wt% silicon.

7. The device of claim 1, wherein the anode comprises no greater than 10 wt% lithium metal, or no greater than 5 wt% lithium metal, or 0 wt% lithium metal.

8. The device of claim 1, wherein the ratio of the amount of cobalt in moles in the cathode active material over the total amount of transition metals in moles in the cathode active material is no more than 0.1, or no more than 0.05, or no more than 0.02, or no more than 0.01, or zero, wherein optionally the transition metals in the cathode active material consist of Ni, Co, Mn, and Fe.

9. The device of claim 1, wherein the ratio of the amount of Mn in moles in the cathode active material over the total amount of transition metals in moles in the cathode active material is no less than 0.3, or no less than 0.4, or no less than 0.5, or no less than 0.6, or no less than 0.7, or no less than 0.8, or no less than 0.9, or equal to 1, wherein optionally the transition metals in the cathode active material consist of Mn, Fe, Co. and Ni.

10. The device of claim 1, wherein the cathode comprises 100 wt% of LMFP, or wherein the cathode comprises LMFP in the range of from 80 wt% to 20 wt%.

11. The device of claim 1, wherein the cathode also comprises a compound of nickel manganese cobalt oxide (NMC) in the range of from 20 wt% to 80 wt%.

12. The device of claim 1, wherein the solvent also comprises a linear ester (R1-CO2-R2), wherein the percentage of the linear ester in the solvent is no more than 20 wt%.

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

14. The device of claim 13, wherein the LiFSI or LiPF6 combined are present at a concentration of from about 0.2 to about 5.0 moles of LiFSI or LiPF6 per kilogram of solvent or at a concentration of from about 0.8 mole to about 2.0 moles of LiFSI or LiPF6 per kilogram of solvent.

15. The device of claim 13, wherein the LiFSI or LiPF6 combined are present in the electrolyte at a percentage in the range of from about 1 wt% to about 30 wt% of the electrolyte or at a percentage in the range of from about 10 wt% to about 25 wt% of the electrolyte.

16. The device of claim 1, wherein the electrolyte comprises no more than 20 wt% ethylene carbonate (EC), or no more than 10 wt% EC, or no more than 5 wt% EC, or no more than 1 wt% EC, or 0 wt% EC.

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

18. The device of claim 1, wherein the percentage of linear carbonate in the electrolyte is no more than 90 wt% or no more than 80 wt% or no more than 75 wt% based on the electrolyte weight.

19. The device of claim 1, wherein the sulfonamide comprises N, N- dimethyltrifluoromethane-sulfonamide (DMTMSA), Diethylsulfamoyl fluoride (DESF), Dimethylsulfamoyl fluoride (DMSF), N-ethyl-N-methyl sulfamoyl fluoride (EMSF), N-methyl sulfamoyl fluoride (MSF), bis(2-methoxyethyl)sulfamoyl fluoride (BMSF), diethylsulfamoyl fluoride (DESF), N-butyl-N, N 0, N O-trimethylsulfamide (BTMSA), or combinations thereof.

20. The device of claim 1, wherein the percentage of sulfonamide in the electrolyte is no less than 1 wt% or no less than 5or from 10 wt% to 30 wt%.

21. The device of claim 1, wherein the salt is selected from the group consisting of lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI), lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), lithium triflouromethanesulfonate or lithium triflate (LiTF), lithium bis(pentafluoroethanesulfonyl)imide (LiBETI), lithium tetracyanoborate (LiB(CN)4), lithium bis(oxalato)borate (LiBOB), lithium difluorooxalatoborate (LiDFOB), and combinations thereof.

22. An electrolyte composition comprisinga cyclic carbonate ester in the range of from 0 wt% to 15 wt%,a sulfonamide in the range of from 40 wt% to 5 wt%,a linear carbonate in the range of from 30 wt% to 85 wt%,a lithium salt selected from the group consisting of LiPFe, LiBF4, LiFSI, and combination thereof, wherein the percentage of the lithium salt in the electrolyte composition is in the range of from 10 wt% to 30 wt%, anda first additive selected from the group consisting of vinylene carbonate (VC), vinyl ethylene carbonate (VEC), vinyl ethylene sulfite (VES), propanesultone (PS), fluoroethylene carbonate (FEC), or combinations thereof, wherein the percentage of the first additive in the electrolyte composition is no less than 0.1 wt%,a second additive selected from the group consisting of lithium bis(oxalato)borate (LiBOB), lithium difluoro(oxalato)borate (LiDFOB), Lithium Difluorophosphate (LiDFP), Lithium difluoro(bisoxalato) phosphate (LiDFOP), Lithium tetrafluoro(bisoxalato) phosphate (LiTFOP), or combinations thereof, wherein the percentage of the second additive in the electrolyte composition is no less than 0.1 wt%.

23. The composition of claim 22, wherein the sulfonamide comprises N, N- dimethyltrifluoromethane-sulfonamide (DMTMSA), diethylsulfamoyl fluoride (DESF) or Dimethylsulfamoyl fluoride (DMSF), N-ethyl-N-methyl sulfamoyl fluoride (EMSF), N-methylsulfamoyl fluoride (MSF), bis(2-methoxyethyl)sulfamoyl fluoride (BMSF), diethylsulfamoyl fluoride (DESF), N-butyl-N, N 0, N 0- trimethylsulfamide (BTMSA), or combinations thereof.

24. The composition of claim 22 comprising no more than 20 wt% ethylene carbonate (EC), or no more than 10 wt% EC, or no more than 5 wt% EC, or no more than 1 wt% EC, or 0 wt% EC.

25. The composition of claim 22, wherein the linear carbonate comprises ethyl methyl carbonate (EMC), dimethyl carbonate (DMC). diethyl carbonate (DEC), or combinations thereof.

26. The composition of claim 22 comprising a third additive selected from the group consisting of 1,3, 2-dioxathiane-2,2-di oxide (TMS), l,3,2-dioxathiolane-2,2-dioxide (DTD), succinic anhydride (SA), prop-l-ene 1,3-sultone (PES), maleic anhydride (MA), triallyl phosphate (TAP), hexamethylene diisocyanate (HDI), methylene methanedisulfonate (MMDS), tris(trimethylsilyl)phosphite (TMSPi), tris(trimethylsilyl)phosphate (TMSPa), 1,3-propanesultone, ethylene sulfite (ES), tris(trimethylsilyl) Borate (TMSB), trimethyl borate (TMO), a nitrile, and combinations thereof, wherein the percentage of the third additive in the electrolyte composition is in the range of from 0.1 wt% to 5 wt%.

27. The composition of claim 26, wherein the nitrile comprises Succinonitrile (SN), Adiponitrile (ADN), 1,3,6-Hexanetricarbonitrile (HTCN), or combinations thereof.

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