Novel battery system based on lithium difluorophosphate

Abstract

To provide a lithium ion battery including two-additive electrolyte systems that enhance performance and lifetime of batteries while reducing costs.SOLUTION: A lithium-ion battery includes a negative electrode, a positive electrode and a nonaqueous electrolyte containing a lithium salt, a nonaqueous solvent and an additive mixture. The nonaqueous solvent contains methyl acetate, and a carbonate solvent selected from among ethylene carbonate, ethyl methyl carbonate, dimethyl carbonate and these combinations. The additive mixture contains: a first operative additive containing a sulfur-containing additive selected from the group consisting of 1,3,2-dioxathiolane 2,2-dioxide, methylene methane disulfonate, trimethylene sulfate, 3-hydroxypropanesulfonic acid γ-sultone and glycol sulfite; and a second operative additive containing vinylene carbonate. The concentration of each of a first operative additive and a second operative additive is 0.25-6 wt.%.SELECTED DRAWING: Figure 46D

Description

[Technical Field]

[0001] The present disclosure relates to rechargeable battery systems, and more particularly to rechargeable lithium-ion battery systems. Such systems include active electrolyte additives and electrodes for improving the properties of the system. Concerning the chemical properties of [Background technology]

[0002] Rechargeable batteries are an integral part of energy storage systems for electric vehicles and grid storage. component (e.g., as part of a microgrid, providing backup power during power outages) Li-ion based batteries are a common type of rechargeable battery.

[0003] Electrolyte additives are effective in improving the life and performance of Li-ion based batteries For example, Non-Patent Document 1 lists five undisclosed proprietary electrolyte additives improve cycle life compared to electrolytes with only one additive or no additives Other studies have shown that three or The focus is on the performance gains from electrolyte systems containing four additives. Researchers typically develop materials that work synergistically with the electrolyte and specific cathodes and anodes. Therefore, the interaction between different additives in a particular system is not understood. The composition of the formulation is often based on trial and error and cannot be predicted in advance.

[0004] Previous work has demonstrated robust systems with sufficient performance for grid or automotive applications. 2. Additive electrolytes that can be incorporated into lithium-ion battery systems to produce The system is not specified. As discussed in Patent Document 1, the two additive systems under study (e.g., 2% VC + 1% allyl methanesulfonate and 2% PES + 1% TTS) Pi) typically performed less well than 3- or 4-additive electrolyte systems (e.g., (See Tables 1 and 2 in Patent Document 1.) Patent Document 1 describes a robust lithium-ion battery system. To create the phosphate buffer, a third compound, often trisphosphate, is added at a concentration of 0.25 to 3 wt%. (trimethylsilyl) (TTSP) or tris(trimethylsilyl) phosphite (TTS Pi) was required (see, for example, paragraph 72 of Patent Document 1). However, additives are expensive and difficult to incorporate into Li-ion batteries on a manufacturing scale. This may lead to simpler yet more effective battery systems that contain fewer additives. It is needed. Summary of the Invention [Means for solving the problem]

[0005] The present disclosure provides a method for storing energy in different energy storage applications, such as in vehicles and grid storage. The present invention is directed to a novel battery system having fewer effective electrolyte additives that can be used. Specifically, the present disclosure provides cost savings over other systems that rely on more additives. Contains a two-additive electrolyte system that improves the performance and life of Li-ion batteries while The present disclosure also provides a method for preparing a two-additive electrolyte system to provide further system enhancements. Also disclosed are effective positive and negative electrodes that cooperate with the system.

[0006] The disclosed two active additive electrolyte systems are: 1) 1,3,2-dioxathiolane-2, 2-dioxide (DTD, also known as ethylene sulfate) or another sulfur-containing Additives (methylenemethane disulfate, trimethylene sulfate, 3-hydroxypropyl sulfur-containing additives, such as propanesulfonic acid gamma sultone, glycol sulfite, or another sulfur-containing additive. 1) Vinylene carbonate (VC) in combination with DTD or another sulfur-containing additive Fluoroethylene carbonate (FEC), and 3) DTD or another sulfur-containing It also contains prop-1-ene-1,3-sultone (PES) in combination with organic additives. VC and FEC provide similar improvements (and are thought to perform similarly). In this case, the mixture of VC and FEC may be considered as a single effective electrolyte. Another two-effective additive electrolyte system shown is in combination with DTD or another sulfur-containing additive. Larger battery systems (electrolytes, electrolyte solvents) contain a mixture of VC and FEC. When used as part of a battery (including the cathode, cathode, and anode), these two effective additives The system offers desirable properties for energy storage applications, including vehicle and grid applications. vinegar.

[0007] More specifically, a lithium nickel manganese cobalt oxide (NMC) cathode and a graphite anode. a lithium salt dissolved in an organic or non-aqueous solvent, which may include methyl acetate (MA), and Two additives to form battery systems with desirable properties for different applications. The solvent may be the following solvents, either alone or in combination: ethylene carbonate (EC), Ethyl methyl carbonate (EMC), methyl acetate, propylene carbonate, dimethyl Carbonates, diethyl carbonate, other carbonate solvents (cyclic or acyclic), other an organic solvent, and / or another non-aqueous solvent. The solvent is present in a higher concentration than the additive, usually a heavy The solvent is present in a concentration greater than 6% by weight. To form the system, two additive pairs (VC and DTD, FEC and DTD, VC and a mixture of FEC and DTD, or another combination). The poles are coated with aluminum oxide (Al2O3), titanium dioxide (TiO2), or another Additionally, to reduce costs, the anode may be made from natural graphite. However, depending on the price structure, artificial graphite may be more cost-effective than natural graphite in certain cases. It is cheaper than

[0008] The present disclosure demonstrates the symbiotic nature of two additive electrolyte systems and selected electrodes. This is supported by experimental data. An exemplary battery system is shown with two additives (e.g., For example, FEC, VC, or PES and DTD or another sulfur-based additive), graphite negative electrode (naturally occurring graphite or synthetic graphite), NMC cathode, lithium electrolyte (even For example, it is formed from a lithium salt such as lithium hexafluorophosphate with the chemical composition LiPF6. ), and an organic or non-aqueous solvent. Lithium-ion batteries consist of a negative electrode and a microelectrode. A cathode comprising NMC having torr-scale particles and a lithium-ion battery having a first non-aqueous solvent. Muion, and either fluoroethylene carbonate or vinylene carbonate the first active ingredient and 1,3,2-dioxathiolane-2,2-dioxide, another sulfur Has a second active additive of either a yellow-containing additive or lithium difluorophosphate a non-aqueous electrolyte comprising the additive mixture. [Brief explanation of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic diagram of a vehicle including a power storage system.

[0010] [Figure 2] FIG. 1 is a schematic diagram of an exemplary power storage system.

[0011] [Figure 3] FIG. 1 is a schematic diagram of a lithium-ion battery-cell system.

[0012] Figures 4A-4J show the results obtained during ultra-high precision charging experiments of battery systems with different electrolyte compositions. Typical experimental data collected are shown below.

[0013] [Figure 4A] FIG. 1 shows time-normalized coulombic inefficiency per hour (CIE / h) versus cycle number for electrolyte systems containing 1% DTD, 2% VC, and 2% VC+1% DTD.

[0014] [Figure 4B] FIG. 1 shows the coulombic efficiency (CE) versus cycle number for electrolyte systems containing 1% DTD, 2% VC, and 2% VC+1% DTD.

[0015] [Figure 4C] FIG. 1 shows the end-of-charge capacity plotted against cycle number for electrolyte systems containing 1% DTD, 2% VC, and 2% VC+1% DTD.

[0016] [Figure 4D] FIG. 1 shows discharge capacity versus cycle number for electrolyte systems containing 1% DTD, 2% VC, and 2% VC+1% DTD.

[0017] [Figure 4E] FIG. 1 shows the change in open circuit voltage versus cycle number for electrolyte systems containing 1% DTD, 2% VC, and 2% VC+1% DTD.

[0018] [Figure 4F] FIG. 1 shows time-normalized coulombic inefficiency per hour (CIE / h) versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, and 2% FEC+1% DTD.

[0019] [Figure 4G] FIG. 1 shows the coulombic efficiency (CE) versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, and 2% FEC+1% DTD.

[0020] [Figure 4H] FIG. 1 shows the end-of-charge capacity plotted against cycle number for electrolyte systems containing 1% DTD, 2% FEC, and 2% FEC+1% DTD.

[0021] [Figure 4I] FIG. 1 shows discharge capacity versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, and 2% FEC+1% DTD.

[0022] [Figure 4J] FIG. 1 shows the average charge voltage and the difference between the average charge voltages (Delta V) versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, and 2% FEC+1% DTD.

[0023] Figures 5A-5C show the average of the last three cycles of the data shown in Figure 4, FEC, Compared with either VC or DTD, FEC+DTD and VC+D TD combinations with lower coulomb inefficiency per hour and lower It shows slippage.

[0024] [Figure 5A] FIG. 5 shows the average coulomb inefficiency per hour for the last three cycles of data generated during the experiment shown in FIG. 4.

[0025] [Figure 5B] FIG. 5 shows the average fragment slippage for the last three cycles of data generated during the experiment shown in FIG. 4.

[0026] [Figure 5C] FIG. 5 shows the average fragment fade for the last three cycles of data generated during the experiment shown in FIG. 4.

[0027] Figures 6A-6F show the results of the analysis using DTD as an additive to electrolyte systems containing VC or FEC. Long-term cycling studies at 40°C / 3CCCV demonstrate the benefits of including Representative experimental data are presented.

[0028] [Figure 6A] FIG. 1 shows capacity versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, 2% FEC+1% DTD, 2% VC, and 2% VC+1% DTD cycled between 3.0 V and 4.2 V.

[0029] [Figure 6B] FIG. 1 shows normalized capacity versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, 2% FEC+1% DTD, 2% VC, and 2% VC+1% DTD cycled between 3.0 V and 4.2 V.

[0030] [Figure 6C] FIG. 1 shows voltage hysteresis (difference between average charging voltage and average charging voltage) versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, 2% FEC+1% DTD, 2% VC, and 2% VC+1% DTD cycled between 3.0 V and 4.2 V.

[0031] [Figure 6D]FIG. 1 shows capacity versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, 2% FEC+1% DTD, 2% VC, and 2% VC+1% DTD cycled between 3.0 V and 4.2 V.

[0032] [Figure 6E] FIG. 1 shows normalized capacity versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, 2% FEC+1% DTD, 2% VC, and 2% VC+1% DTD cycled between 3.0 V and 4.2 V.

[0033] [Figure 6F] FIG. 1 shows voltage hysteresis (difference between average charging voltage and average charging voltage) versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, 2% FEC+1% DTD, 2% VC, and 2% VC+1% DTD cycled between 3.0 V and 4.2 V.

[0034] Figures 7A-7F show the results of the analysis using DTD as an additive to electrolyte systems containing VC or FEC. Long-term cycling studies at 20°C / 3CCCV demonstrate the benefits of including Representative experimental data are presented.

[0035] [Figure 7A] FIG. 1 shows capacity versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, 2% FEC+1% DTD, 2% VC, and 2% VC+1% DTD cycled between 3.0 V and 4.3 V.

[0036] [Figure 7B] FIG. 1 shows normalized capacity versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, 2% FEC+1% DTD, 2% VC, and 2% VC+1% DTD cycled between 3.0 V and 4.3 V.

[0037] [Figure 7C]FIG. 1 shows voltage hysteresis (difference between average charging voltage and average charging voltage) versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, 2% FEC+1% DTD, 2% VC, and 2% VC+1% DTD cycled between 3.0 V and 4.3 V.

[0038] [Figure 7D] FIG. 1 shows capacity versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, 2% FEC+1% DTD, 2% VC, and 2% VC+1% DTD cycled between 3.0 V and 4.3 V.

[0039] [Figure 7E] FIG. 1 shows normalized capacity versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, 2% FEC+1% DTD, 2% VC, and 2% VC+1% DTD cycled between 3.0 V and 4.3 V.

[0040] [Figure 7F] FIG. 1 shows voltage hysteresis (difference between average charging voltage and average charging voltage) versus cycle number for electrolyte systems containing 1% DTD, 2% FEC, 2% FEC+1% DTD, 2% VC, and 2% VC+1% DTD cycled between 3.0 V and 4.3 V.

[0041] 8A-8I show graphs of electrolyte composition collected during cycling experiments according to certain embodiments of the present disclosure. Typical empirical data are shown below.

[0042] [Figure 8A] Figure 1 shows peak capacity versus cycle number for electrolyte systems containing 2% FEC, 1% FEC + 1% DTD, 2% FEC + 1% DTD, 1% FEC + 1% MMDS, and 2% FEC + 1% MMDS cycled between 3.0 V and 4.3 V at 40 °C in a base electrolyte of 1.2 M LiPF in 30% ethylene carbonate and 70% ethyl methyl carbonate.

[0043] [Figure 8B] FIG. 1 shows normalized capacity versus cycle number for electrolyte systems containing 2% FEC, 1% FEC + 1% DTD, 2% FEC + 1% DTD, 1% FEC + 1% MMDS, and 2% FEC + 1% MMDS cycled between 3.0 V and 4.3 V at 40° C. in a base electrolyte of 1.2 M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate.

[0044] [Figure 8C] Figure 1 shows the voltage hysteresis (difference between average charge voltage and average charge voltage) for electrolyte systems containing 2% FEC, 1% FEC + 1% DTD, 2% FEC + 1% DTD, 1% FEC + 1% MMDS, and 2% FEC + 1% MMDS cycling between 3.0 V and 4.3 V at 40 °C in a base electrolyte of 1.2 M LiPF in 30% ethylene carbonate and 70% ethyl methyl carbonate.

[0045] [Figure 8D] Figure 1 shows peak capacity versus cycle number for electrolyte systems containing 2% VC, 1% VC + 1% DTD, 2% VC + 1% DTD, 1% VC + 1% MMDS, and 2% VC + 1% MMDS cycled between 3.0 V and 4.3 V at 40 °C in a base electrolyte of 1.2 M LiPF in 30% ethylene carbonate and 70% ethyl methyl carbonate.

[0046] [Figure 8E] Figure 1 shows normalized capacity versus cycle number for electrolyte systems containing 2% VC, 1% VC + 1% DTD, 2% VC + 1% DTD, 1% VC + 1% MMDS, and 2% VC + 1% MMDS cycled between 3.0 V and 4.3 V at 40 °C in a base electrolyte of 1.2 M LiPF in 30% ethylene carbonate and 70% ethyl methyl carbonate.

[0047] [Figure 8F]Figure 1 shows the voltage hysteresis (difference between average charge voltage and average charge voltage) for electrolyte systems containing 2% FEC, 1% VC + 1% DTD, 2% VC + 1% DTD, 1% VC + 1% MMDS, and 2% VC + 1% MMDS cycling between 3.0 V and 4.3 V at 40 °C in a base electrolyte of 1.2 M LiPF in 30% ethylene carbonate and 70% ethyl methyl carbonate by weight.

[0048] [Figure 8G] Figure 1 shows peak capacity versus cycle number for electrolyte systems containing 2% PES, 1% PES + 1% DTD, 2% PES + 1% DTD, 1% PES + 1% MMDS, and 2% PES + 1% MMDS cycled between 3.0 V and 4.3 V at 40 °C in a base electrolyte of 1.2 M LiPF in 30% ethylene carbonate and 70% ethyl methyl carbonate.

[0049] [Figure 8H] FIG. 1 shows normalized capacity versus cycle number for electrolyte systems containing 2% PES, 1% PES+1% DTD, 2% PES+1% DTD, 1% PES+1% MMDS, and 2% PES+1% MMDS cycled between 3.0 V and 4.3 V at 40° C. in a base electrolyte of 1.2 M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate.

[0050] [Figure 8I] Figure 1 shows the voltage hysteresis (difference between average charge voltage and average charge voltage) for electrolyte systems containing 2% FEC, 1% PES + 1% DTD, 2% PES + 1% DTD, 1% PES + 1% MMDS, and 2% PES + 1% MMDS cycled between 3.0 V and 4.3 V at 40 °C in a base electrolyte of 1.2 M LiPF in 30% ethylene carbonate and 70% ethyl methyl carbonate.

[0051] 9A to 9D and 9F to 9I show that electrolyte conductivity can be increased without significantly sacrificing lifetime. First, acetic acid was added to the electrolyte system containing VC or FEC with DTD to reduce the viscosity. Typical results collected during some ultra-precise charging experiments show that methyl methyl phosphate can be added. The experimental data shows that the improved conductivity and reduced viscosity are beneficial for certain applications requiring higher charging rates. It is important for the future.

[0052] [Figure 9A] 1 is exemplary experimental data showing coulombic efficiency (CE) versus cycle number for an electrolyte system according to certain embodiments of the present disclosure.

[0053] [Figure 9B] 1 is exemplary experimental data showing end-of-charge capacity plotted against cycle number for an electrolyte system according to certain embodiments of the present disclosure.

[0054] [Figure 9C] 1 is exemplary experimental data showing discharge capacity versus cycle number for an electrolyte system according to certain embodiments of the present disclosure.

[0055] [Figure 9D] 1 is exemplary experimental data showing the difference between the average charge voltage at the open circuit voltage and the average charge voltage (Delta V) versus cycle number for an electrolyte system according to certain embodiments of the present disclosure.

[0056] [Figure 9F] 1 is exemplary experimental data of coulombic efficiency (CE) versus cycle number for an electrolyte system according to certain embodiments of the present disclosure.

[0057] [Figure 9G] 1 is exemplary experimental data of end-of-charge capacity plotted against cycle number for an electrolyte system according to certain embodiments of the present disclosure.

[0058] [Figure 9H]1 is exemplary experimental data of discharge capacity versus cycle number for an electrolyte system according to certain embodiments of the present disclosure.

[0059] [Figure 9I] 10 is exemplary experimental data of average charge voltage to average charge voltage difference (Delta V) versus cycle number for electrolyte systems according to certain embodiments of the present disclosure.

[0060] Figures 10A-10C are plots summarizing the experimental data, showing the relationship between the MA content and the solubility of the solubility of the MA content. However, the electrolyte additives VC and FEC still showed no significant effects, either alone or in the presence of DTD. It has been shown to provide acceptable performance.

[0061] [Figure 10A] 1 is a plot summarizing experimental data of time-normalized CIE as a function of MA content.

[0062] [Figure 10B] 1 is a plot summarizing experimental data of time-normalized fragment fade as a function of MA content.

[0063] [Figure 10C] 1 is a plot summarizing time-normalized fractional end-of-charge capacity slip as a function of MA content.

[0064] [Figure 11] 10 is a plot summarizing experimental data of parasitic heat flow, and the difference between the parasitic heat flow and the parasitic heat flow of a cell containing 2% FEC + 0% MA, as a function of voltage for different electrolyte compositions containing FEC in the voltage range of 4.0 V to 4.2 V.

[0065] [Figure 12]Figure 12A shows plots summarizing experimental data for parasitic heat flow, and the difference between the parasitic heat flow and the parasitic heat flow of a cell containing 2% FEC + 0% MA, as a function of voltage for different electrolyte compositions containing FEC in the voltage range of 4.0 V to 4.3 V. Figure 12A shows the results from the first cycle up to 4.3 V. Figure 12B shows the results from the second cycle.

[0066] [Figure 13] 10 is a plot summarizing experimental data of parasitic heat flow, and the difference between the parasitic heat flow and the parasitic heat flow of a cell containing 2% FEC + 0% MA, as a function of voltage for different electrolyte compositions containing FEC in the voltage range of 4.0 V to 4.4 V. [Figure 13A] Results from the first cycle up to 4.4V are shown. [Figure 13B] The results of the second cycle are shown.

[0067] [Figure 14] 14 is a plot summarizing experimental parasitic heat flow data, including the data shown in FIGS. 11-13.

[0068] 15A-15F show the capacitance, normalized capacitance, and potential of the electrolyte system containing FEC. Voltage hysteresis (difference between average charging voltage and average charging voltage) vs. cycle number obtained at 20°C 1 is a plot of experimental data.

[0069] [Figure 15A] 1 is a plot of experimental data obtained at 20° C. for an electrolyte system containing FEC cycled up to 4.2 V versus capacity versus cycle number.

[0070] [Figure 15B] 1 is a plot of experimental data obtained at 20° C. of normalized capacity versus cycle number for electrolyte systems containing FEC cycled up to 4.2 V.

[0071] [Figure 15C]1 is a plot of experimental data obtained at 20° C. of voltage hysteresis (difference between average charge voltage and average charge voltage) versus cycle number for electrolyte systems containing FEC cycled up to 4.2 V.

[0072] [Figure 15D] 1 is a plot of experimental data obtained at 20° C. of capacity versus cycle number for an electrolyte system containing FEC cycled up to 4.3 V.

[0073] [Figure 15E] 1 is a plot of experimental data obtained at 20° C. of normalized capacity versus cycle number for an electrolyte system containing FEC cycled up to 4.3 V.

[0074] [Figure 15F] 1 is a plot of experimental data obtained at 20° C. of voltage hysteresis (difference between average charge voltage and average charge voltage) versus cycle number for electrolyte systems containing FEC cycled up to 4.3 V.

[0075] 16A-16F show the capacitance, normalized capacitance, and potential of the electrolyte system containing FEC. 1 is a plot of experimental data obtained at 40° C. of pressure hysteresis.

[0076] [Figure 16A] 1 is a plot of experimental data obtained at 40° C. for an electrolyte system containing FEC cycled up to 4.2 V versus capacity versus cycle number.

[0077] [Figure 16B] 1 is a plot of experimental data obtained at 40° C. of normalized capacity versus cycle number for an electrolyte system containing FEC cycled up to 4.2 V.

[0078] [Figure 16C]1 is a plot of experimental data obtained at 40° C. of voltage hysteresis (difference between average charge voltage and average charge voltage) versus cycle number for electrolyte systems containing FEC cycled up to 4.2 V.

[0079] [Figure 16D] 1 is a plot of experimental data obtained at 40° C. for an electrolyte system containing FEC cycled up to 4.3 V versus capacity versus cycle number.

[0080] [Figure 16E] 1 is a plot of experimental data obtained at 40° C. of normalized capacity versus cycle number for an electrolyte system containing FEC cycled up to 4.3 V.

[0081] [Figure 16F] 1 is a plot of experimental data obtained at 40° C. of voltage hysteresis (difference between average charge voltage and average charge voltage) versus cycle number for electrolyte systems containing FEC cycled up to 4.3 V.

[0082] 17A-17F show the results of electrolytic systems containing FEC, VC, and / or DTD. 1 is a plot of experimental data for capacitance, normalized capacitance, and voltage hysteresis.

[0083] [Figure 17A] 10 is a plot of experimental data of capacity versus cycle number for electrolyte systems containing FEC and / or DTD cycled up to 4.3V.

[0084] [Figure 17B] 1 is a plot of experimental data of normalized capacity versus cycle number for electrolyte systems containing FEC and / or DTD cycled up to 4.3V.

[0085] [Figure 17C]1 is a plot of experimental data of voltage hysteresis (difference between average charge voltage and average charge voltage) versus cycle number for electrolyte systems containing FEC and / or DTD cycled up to 4.3V.

[0086] [Figure 17D] 10 is a plot of experimental data of capacity versus cycle number for electrolyte systems containing VC and / or DTD cycled up to 4.3 V.

[0087] [Figure 17E] 10 is a plot of experimental data of normalized capacity versus cycle number for electrolyte systems containing VC and / or DTD cycled up to 4.3 V.

[0088] [Figure 17F] 1 is a plot of experimental data of voltage hysteresis (difference between average charge voltage and average charge voltage) versus cycle number for electrolyte systems containing VC and / or DTD cycled up to 4.3 V.

[0089] [Figure 18A] 1 is a plot of experimental data of capacity versus cycle number for electrolyte systems containing FEC cycled up to 4.3V.

[0090] [Figure 18B] 1 is a plot of experimental data of normalized capacity versus cycle number for electrolyte systems containing FEC cycled up to 4.3V.

[0091] [Figure 19] 1 is a plot of experimental data of voltage hysteresis (difference between average charge voltage and average charge voltage) versus cycle number for electrolyte systems containing FEC cycled up to 4.3V.

[0092] [Figure 20] 1 is a plot summarizing experimental data of the volume of forming gas produced during cell formation for different electrolyte systems.

[0093] [Figure 21] 1 is a plot summarizing experimental data for charge transfer impedance for different electrolyte systems.

[0094] [Figure 22] 1 is a plot summarizing experimental data measuring slow capacity loss for different electrolyte systems after cells are charged at three different charge rates for 30 cycles at 20° C.

[0095] [Figure 23] 1 is a plot summarizing experimental data summarizing peak capacity as a function of cycle number for different electrolyte systems used in cells charged at different charge rates at 20° C.

[0096] [Figure 24] 1 is a plot summarizing experimental data summarizing peak capacity as a function of cycle number for different electrolyte systems used in cells charged at different charge rates at 20° C.

[0097] [Figure 25] 1 is a plot summarizing experimental data of the volume of gas formed for different additives in MA solvent at various concentrations.

[0098] [Figure 26] 1 is a plot summarizing experimental data of charge transfer impedance for different additives in electrolytes containing various concentrations of MA solvent.

[0099] [Figure 27] 1 is a plot summarizing experimental data of slow capacity loss after 30 cycles of charging at 1, 1.5, and 2 C at 20° C. with different electrolyte compositions.

[0100] [Figure 28] FIG. 28 is an expanded view of certain experimental data shown in FIG. 27.

[0101] [Figure 29] FIG. 1 summarizes experimental data for delta-V (difference between average charge voltage and average charge voltage) as a function of cycle number for electrolyte systems containing FEC.

[0102] [Figure 30] FIG. 1 summarizes experimental data for peak capacity as a function of cycle number for electrolyte systems containing FEC.

[0103] [Figure 31] FIG. 11 summarizes experimental data for energy hysteresis as a function of cycle number for electrolyte systems containing FEC.

[0104] [Figure 32] FIG. 11 summarizes experimental data for delta-V (difference between average charging voltage and average charging voltage) as a function of cycle number for electrolyte systems containing VC.

[0105] [Figure 33] FIG. 1 summarizes experimental data of peak capacity as a function of cycle number for electrolyte systems containing VC.

[0106] [Figure 34] FIG. 11 summarizes experimental data of energy hysteresis as a function of cycle number for electrolyte systems containing VC.

[0107] 35A-35D show the results of an electrolyte system with a positive electrode of NMC532 and a negative electrode of synthetic graphite. This article summarizes experimental data from the system.

[0108] [Figure 35A] FIG. 11 summarizes experimental impedance data by plotting the real part of the impedance against the negative imaginary part of the impedance for different electrolyte systems, including systems containing LFOs.

[0109] [Figure 35B] Figure 1 summarizes experimental impedance data by plotting the negative imaginary part of the impedance against the real part of the impedance for different electrolyte systems, including those containing VC, PES, or LFO.

[0110] [Figure 35C] FIG. 11 summarizes experimental impedance data by plotting the negative imaginary part of the impedance against the real part of the impedance for different electrolyte systems, including systems containing FEC, DTD, or LFO.

[0111] [Figure 35D] Figure 1 summarizes experimental impedance data for different electrolyte systems containing VC, FEC, DTD, PES, or LFO, a positive electrode of NMC532, and a negative electrode of synthetic graphite.

[0112] [Figure 36] Figure 1 summarizes the experimental data for different electrolyte systems containing VC, FEC, DTD, PES, or LFO.

[0113] 37A-37F show the results of different electrolytes containing LFO compared to a control without LFO. Experimental storage data for the system are summarized.

[0114] [Figure 37A] FIG. 11 summarizes the voltage drop data for different electrolyte systems containing LFO compared to a control without LFO after storing the systems at 4.4 V for 500 hours at 60° C.

[0115] [Figure 37B] FIG. 11 summarizes the voltage drop data for different electrolyte systems containing LFO compared to a control without LFO after storing the systems at 2.5 V for 500 hours at 60° C.

[0116] [Figure 37C]FIG. 11 summarizes the volume change data for different electrolyte systems containing LFO compared to a control without LFO after storing the systems at 4.4 V for 500 hours at 60° C.

[0117] [Figure 37D] FIG. 11 summarizes the volume change data for different electrolyte systems containing LFO compared to a control without LFO after storing the systems at 2.5 V for 500 hours at 60° C.

[0118] [Figure 37E] FIG. 10 summarizes the impedance data for different electrolyte systems containing LFO compared to a control without LFO, before and after storing the systems at 4.4 V for 500 hours at 60° C.

[0119] [Figure 37F] FIG. 11 summarizes the impedance data for different electrolyte systems containing LFO compared to a control without LFO, before and after storing the systems at 2.5 V for 500 hours at 60° C.

[0120] 38A-38F show the results of different electrolytes containing LFO compared to a control without LFO. Experimental storage data for the system are summarized.

[0121] [Figure 38A] FIG. 11 summarizes the voltage drop data for different electrolyte systems containing LFO compared to a control without LFO after storing the systems at 4.4 V for 500 hours at 60° C.

[0122] [Figure 38B] FIG. 11 summarizes the voltage drop data for different electrolyte systems containing LFO compared to a control without LFO after storing the systems at 2.5 V for 500 hours at 60° C.

[0123] [Figure 38C]FIG. 11 summarizes the volume change data for different electrolyte systems containing LFO compared to a control without LFO after storing the systems at 4.4 V for 500 hours at 60° C.

[0124] [Figure 38D] FIG. 11 summarizes the volume change data for different electrolyte systems containing LFO compared to a control without LFO after storing the systems at 2.5 V for 500 hours at 60° C.

[0125] [Figure 38E] FIG. 10 summarizes the impedance data for different electrolyte systems containing LFO compared to a control without LFO, before and after storing the systems at 4.4 V for 500 hours at 60° C.

[0126] [Figure 38F] FIG. 11 summarizes the impedance data for different electrolyte systems containing LFO compared to a control without LFO, before and after storing the systems at 2.5 V for 500 hours at 60° C.

[0127] 39A-39F show the results of different electrolytes containing LFO compared to a control without LFO. The experimental data of the system is summarized.

[0128] [Figure 39A] FIG. 11 summarizes data on coulombic efficiency (CE) versus cycle number for electrolyte systems, including systems with LFO, cycled to 4.1 V.

[0129] [Figure 39B] FIG. 11 summarizes data on voltage change versus cycle number for different electrolyte systems, including systems with LFO, cycled to 4.1 V.

[0130] [Figure 39C]FIG. 10 summarizes the end-of-charge capacity data plotted against cycle number for different electrolyte systems, including systems with LFO, cycled to 4.1 V.

[0131] [Figure 39D] FIG. 10 summarizes normalized discharge capacity versus cycle number data for different electrolyte systems, including systems with LFO, cycled to 4.1 V.

[0132] [Figure 39E] FIG. 10 summarizes data on coulombic efficiency (CE) versus cycle number for electrolyte systems, including systems with LFO, cycled to 4.2 V.

[0133] [Figure 39F] FIG. 11 summarizes data on voltage change versus cycle number for different electrolyte systems, including systems containing LFO, cycled to 4.2 V.

[0134] [Figure 39G] FIG. 11 summarizes data on end-of-charge capacity plotted against cycle number for different electrolyte systems, including systems with LFO, cycled to 4.2 V.

[0135] [Figure 39H] FIG. 11 summarizes normalized discharge capacity versus cycle number data for different electrolyte systems, including systems with LFO, cycled to 4.2 V.

[0136] 40A-40F show the results of different voltages including LFO compared to a control without LFO. The experimental data for the solution system are summarized.

[0137] [Figure 40A] FIG. 11 summarizes the coulombic efficiency (CE) versus cycle number data for electrolyte systems, including systems with LFO, cycled to 4.3 V.

[0138] [Figure 40B] FIG. 11 summarizes data on the change in open circuit voltage versus cycle number for different electrolyte systems, including systems containing LFO, cycled to 4.3 V.

[0139] [Figure 40C] FIG. 11 summarizes data on end-of-charge capacity plotted against cycle number for different electrolyte systems, including systems with LFO, cycled to 4.3 V.

[0140] [Figure 40D] FIG. 11 summarizes normalized discharge capacity versus cycle number data for different electrolyte systems, including systems with LFO, cycled to 4.3 V.

[0141] [Figure 40E] FIG. 11 summarizes data on coulombic efficiency (CE) versus cycle number for electrolyte systems, including systems with LFO, cycled to 4.4 V.

[0142] [Figure 40F] FIG. 11 summarizes data on the change in open circuit voltage versus cycle number for different electrolyte systems, including systems containing LFO, cycled to 4.4 V.

[0143] [Figure 40G] FIG. 11 summarizes data on end-of-charge capacity plotted against cycle number for different electrolyte systems, including systems with LFO, cycled to 4.4 V.

[0144] [Figure 40H] FIG. 11 summarizes normalized discharge capacity versus cycle number data for different electrolyte systems, including systems with LFO, cycled to 4.4 V.

[0145] [Figure 41A]FIG. 11 summarizes data on coulombic inefficiency versus upper cutoff voltage for different electrolyte systems, including systems containing LFO.

[0146] [Figure 41B] FIG. 11 summarizes data on fraction fade versus upper cutoff voltage for different electrolyte systems, including systems with LFOs.

[0147] [Figure 41C] FIG. 11 summarizes data for end-of-charge capacity slip versus upper cutoff voltage for different electrolyte systems, including systems containing LFO.

[0148] [Figure 42A] FIG. 41B is an expanded view of FIG. 41A summarizing data on coulombic inefficiency versus upper cutoff voltage for different electrolyte systems, including systems containing LFO.

[0149] [Figure 42B] 41B is a close-up of the fragment fade versus upper cutoff voltage data for different electrolyte systems, including systems containing LFO.

[0150] [Figure 42C] 41C is a close-up view summarizing the end-of-charge capacity slip versus upper cut-off voltage data for different electrolyte systems, including systems containing LFO.

[0151] 43A-43D show long-term results for different electrolyte systems, including systems containing LFO. This summarizes the icing data.

[0152] [Figure 43A] FIG. 10 summarizes normalized discharge capacity data for different electrolyte systems, including systems with LFO, cycled at 40° C.

[0153] [Figure 43B]FIG. 11 summarizes average charge voltage data for different electrolyte systems, including systems containing LFO, cycled at 40° C.

[0154] [Figure 43C] FIG. 11 summarizes normalized discharge capacity data for different electrolyte systems, including systems containing LFO, cycled at 20° C.

[0155] [Figure 43D] FIG. 11 summarizes average charge voltage data for different electrolyte systems, including systems containing LFO, cycled at 20° C.

[0156] 44A-44D show fast charging of different electrolyte systems, including systems containing LFO. Long-term cycling data under electric current are summarized.

[0157] [Figure 44A] FIG. 10 summarizes normalized discharge capacity data for different electrolyte systems, including systems with LFO, cycled at 20° C. during the first experiment.

[0158] [Figure 44B] FIG. 10 summarizes the average charge voltage data for different electrolyte systems, including systems with LFO, cycled at 20° C. during the first experiment.

[0159] [Figure 44C] FIG. 10 summarizes normalized discharge capacity data for different electrolyte systems, including systems with LFO, cycled at 20° C. during the second experiment.

[0160] [Figure 44D] FIG. 10 summarizes the average charge voltage data for different electrolyte systems, including systems with LFO, cycled at 20° C. during the second experiment.

[0161] [Figure 45A] FIG. 11 summarizes voltage data for different electrolyte systems, including systems with LFO, when the cells were maintained at 40° C.

[0162] [Figure 45B] FIG. 11 summarizes volume change data for different electrolyte systems, including systems containing LFO, when the cells were maintained at 40° C.

[0163] 46A-46D show voltage drop and impedance data generated during storage experiments. It summarizes:

[0164] [Figure 46A] FIG. 10 summarizes voltage drop data for different electrolyte systems, including systems containing LFO, after cells were maintained at 4.4 V for 500 hours at 60° C.

[0165] [Figure 46B] FIG. 10 summarizes impedance data for different electrolyte systems, including systems with LFO, before and after cells were maintained at 4.4 V for 500 hours at 60° C.

[0166] [Figure 46C] FIG. 10 summarizes voltage drop data for different electrolyte systems, including systems containing LFO, after cells were maintained at 2.5 V for 500 hours at 60° C.

[0167] [Figure 46D] FIG. 11 summarizes impedance data for different electrolyte systems, including systems with LFO, before and after cells were maintained at 2.5 V for 500 hours at 60° C.

[0168] [Figure 47] FIG. 1 illustrates exemplary data during specific charging and discharging situations.

[0169] Figures 48A-48F summarize the experimental heat flow data versus voltage. 48B, 48D, and 48E show the results of the first cycle to 4.4 V. , and Figure 48F shows the results of the second cycle to 4.4V.

[0170] [Figure 48A] Figure 10 summarizes experimental parasitic heat flow data as a function of voltage for different electrolyte systems, including systems containing DTD, in the voltage range of 4.0 V to 4.4 V during the first cycle, and the difference between the parasitic heat flow and that of a cell containing 2% VC + 1% DTD.

[0171] [Figure 48B] Figure 10 summarizes experimental parasitic heat flow data as a function of voltage for different electrolyte systems, including systems containing DTD, in the voltage range of 4.0 V to 4.4 V during the second cycle, and the difference between the parasitic heat flow and that of a cell containing 2%VC+1%DTD.

[0172] [Figure 48C] Figure 10 summarizes experimental parasitic heat flow data as a function of voltage for different electrolyte systems, including systems with LFO, in the voltage range of 4.0 V to 4.4 V during the first cycle, and the difference between the parasitic heat flow and that of a cell with 2% VC + 1% DTD.

[0173] [Figure 48D] Figure 10 summarizes experimental parasitic heat flow data as a function of voltage for different electrolyte systems, including systems with LFO, in the voltage range of 4.0 V to 4.4 V during the second cycle, and the difference between the parasitic heat flow and that of a cell with 2% VC + 1% DTD.

[0174] [Figure 48E]Figure 10 summarizes experimental parasitic heat flow data as a function of voltage for different electrolyte systems, including systems with LFO, in the voltage range of 4.0 V to 4.4 V during the first cycle, and the difference between the parasitic heat flow and that of a cell with 2% VC + 1% DTD.

[0175] [Figure 48F] Figure 10 summarizes experimental parasitic heat flow data as a function of voltage for different electrolyte systems, including systems with LFO, in the voltage range of 4.0 V to 4.4 V during the second cycle, and the difference between the parasitic heat flow and that of a cell with 2% VC + 1% DTD.

[0176] 50A-50C show experimental averages as a function of cycle number for different electrolyte systems. The uniform parasitic heat flow data are summarized.

[0177] [Figure 50A] FIG. 10 summarizes experimental average parasitic heat flow data as a function of cycle number for electrolyte systems containing 2% VC+1% DTD and 2% FEC+1% DTD.

[0178] [Figure 50B] Figure 10 summarizes experimental average parasitic heat flow data as a function of cycle number for electrolyte systems containing 0.5% LFO, 1% LFO, 1.5% LFO, 0.5% LFO + 1% VC + 1% FEC, 1.0% LFO + 1% VC + 1% FEC, and 1.5% LFO + 1% VC + 1% FEC.

[0179] [Figure 50C] FIG. 10 summarizes experimental average parasitic heat flow data as a function of cycle number for electrolyte systems containing 1% LFO, 1% LFO+1% VC, 1% LFO+1% FEC, and 1% LFO+1% VC+1% FEC.

[0180] [Figure 51] FIG. 50A-50C summarize the experimental data from FIGS. 50A-C showing the best performing cells from the parasitic heat flow experiments.

[0181] Figures 52A-52D show a no LFO control cycled to 4.2V. Experimental data for different electrolyte systems containing LFO compared to controls are summarized.

[0182] [Figure 52A] FIG. 10 summarizes data on coulombic efficiency versus cycle number for electrolyte systems, including systems with LFO, cycled to 4.2 V.

[0183] [Figure 52B] FIG. 11 summarizes data on end-of-charge capacity plotted against cycle number for different electrolyte systems, including systems with LFO, cycled to 4.2 V.

[0184] [Figure 52C] FIG. 11 summarizes data on voltage change versus cycle number for different electrolyte systems, including systems containing LFO, cycled to 4.2 V.

[0185] [Figure 52D] FIG. 11 summarizes normalized discharge capacity versus cycle number data for different electrolyte systems, including systems with LFO, cycled to 4.2 V.

[0186] Figures 53A-53D show a control with no LFO cycled to 4.3V. Experimental data for different electrolyte systems containing LFO compared to controls are summarized.

[0187] [Figure 53A] FIG. 11 summarizes the coulombic efficiency versus cycle number data for electrolyte systems, including systems with LFO, cycled to 4.3 V.

[0188] [Figure 53B]FIG. 11 summarizes data on end-of-charge capacity plotted against cycle number for different electrolyte systems, including systems with LFO, cycled to 4.3 V.

[0189] [Figure 53C] FIG. 11 summarizes data on voltage change versus cycle number for different electrolyte systems, including systems containing LFO, cycled to 4.3 V.

[0190] [Figure 53D] FIG. 11 summarizes normalized discharge capacity versus cycle number data for different electrolyte systems, including systems with LFO, cycled to 4.3 V.

[0191] Figures 54A-54D show a no LFO control cycled to 4.4V. Experimental data for different electrolyte systems containing LFO compared to controls are summarized.

[0192] [Figure 54A] FIG. 10 summarizes experimental data for coulombic efficiency versus cycle number for electrolyte systems, including systems with LFO, cycled to 4.4 V.

[0193] [Figure 54B] FIG. 10 summarizes experimental data of end-of-charge capacity plotted against cycle number for different electrolyte systems, including systems with LFO, cycled to 4.4 V.

[0194] [Figure 54C] FIG. 10 summarizes experimental data for voltage change versus cycle number for different electrolyte systems, including systems containing LFO, cycled to 4.4 V.

[0195] [Figure 54D] FIG. 10 summarizes experimental data for normalized discharge capacity versus cycle number for different electrolyte systems, including systems with LFO, cycled to 4.4 V.

[0196] [Figure 55A] FIG. 11 summarizes data on coulombic inefficiency versus upper cutoff voltage for different electrolyte systems, including systems containing LFO.

[0197] [Figure 55B] FIG. 11 summarizes data on fraction fade versus upper cutoff voltage for different electrolyte systems, including systems with LFOs.

[0198] [Figure 55C] FIG. 11 summarizes data for end-of-charge capacity slip versus upper cutoff voltage for different electrolyte systems, including systems containing LFO.

[0199] [Figure 56A] FIG. 55B is an expanded view of FIG. 55A summarizing data on coulombic inefficiency versus upper cutoff voltage for different electrolyte systems, including systems containing LFO.

[0200] [Figure 56B] 55B is a close-up of the fragment fade versus upper cutoff voltage data for different electrolyte systems, including systems containing LFO.

[0201] [Figure 56C] FIG. 55C is a zoomed-in view of FIG. 55C summarizing the end-of-charge capacity slip versus upper cutoff voltage data for different electrolyte systems, including systems containing LFO.

[0202] [Figure 57] FIG. 10 shows impedance data generated during an ultra-high precision cyclic experiment.

[0203] Figures 58A-58D show a composite made from NMC622 with two different coatings. 1 summarizes experimental data for an electrolyte system containing LFO with a positive electrode.

[0204] [Figure 58A] FIG. 11 summarizes experimental data of voltage drop after storage at 60° C. for 500 of various electrolyte systems at 4.4 V.

[0205] [Figure 58B] FIG. 11 summarizes experimental data on impedance of 500 of various electrolyte systems at 4.4 V before and after storage at 60° C.

[0206] [Figure 58C] FIG. 11 summarizes experimental data of voltage drop after storage at 60° C. for 500 of various electrolyte systems at 2.5 V.

[0207] [Figure 58D] FIG. 11 summarizes experimental data on impedance of 500 of various electrolyte systems at 2.5 V before and after storage at 60° C.

[0208] [Figure 60] This figure summarizes experimental data on the mass change over time due to air exposure for LFOs from Guangzhou Tinci Materials Technology Co., Ltd. and Shenzhen Capchem Technology Co., Ltd.

[0209] [Figure 61] 1 is a diagram summarizing the experimental data of thermogravimetric analysis of LFO from Guangzhou Tinci Materials Technology Co., Ltd. and Shenzhen Capchem Technology Co., Ltd. DETAILED DESCRIPTION OF THE INVENTION

[0210] FIG. 1 shows the basic components of a battery-powered electric vehicle (EV) 100. The electric vehicle 100 includes at least one drive motor (traction motor) 102A and / or 102B, at least one of the drive motors 102A and / or 102B coupled to the corresponding drive motors 102A and / or 102B. Another gearbox 104A and / or 104B, a battery cell 106, and an electronic Generally, the battery cells 106 power the electronics of the electric vehicle 100. To propel the electric vehicle 100 using the drive motors 102A and / or 102B, The electric vehicle 100 is not described herein but is known to those skilled in the art. The electric vehicle 100 of FIG. Although shown as having four wheels, different electric vehicles may have fewer or more than four wheels. Additionally, different types of electric vehicles 100 may have, among other types of vehicles: This specification also includes, among other things, motorcycle, aircraft, truck, boat and train engines. The present disclosure may incorporate the inventive concepts described in The parts may be used in the automobile 100.

[0211] FIG. 2 is a schematic diagram of an exemplary energy storage system 200 showing various components. The energy storage system 200 typically includes at least one base 202 and four It includes a modular housing having side walls 204 (only two shown). The module housing is generally electrically insulated from the contained battery cells 206. This is achieved through physical separation, through an electrically insulating layer, and through the module housing. Through the selection of insulating materials, any combination of these, or through other methods, The base 202 may be made of polypropylene, polyurethane, polyvinyl chloride, or another Metal sheet or non-conductive material such as plastic, non-conductive composite, or insulating carbon fiber The sidewall 204 may also include an insulating layer or may be an electrically insulating layer on an electrically insulating material. or polypropylene, polyurethane, polyvinyl chloride, other plastics, non-conductive composites The wire may be made of a non-conductive or electrically insulating material, such as a composite material or insulating carbon fiber. One or more interconnect layers 230 are disposed on the battery cells 206, and the top plate 210 is The top plate 210 may be a single plate or may be disposed on the connecting layer 230. Alternatively, it may be formed of a plurality of plates.

[0212] The individual battery cells 106 and 206 often contain an electrolyte containing lithium ions. The lithium-ion battery cell has a positive electrode and a negative electrode. A schematic diagram of a battery 300 is shown. Lithium ions 350 are distributed throughout an electrolyte 320 within a container 360. The container 360 can be part of a battery cell. The lithium ions 350 are dispersed in the positive electrode 330 and the negative electrode 340. A separator 370 separates the negative and positive electrodes. A circuit 310 connects the negative and positive terminals.

[0213] New research by the inventors has led to the development of a novel hybrid powertrain for use in grid and electric vehicle applications. Novel electrolytes and battery systems have been identified. These systems include: 1) 1,3,2-di- Oxathiolane-2,2-dioxide (DTD, also known as ethylene sulfate) ) or vinylene carbonate (VC) in combination with another sulfur-containing additive, 2) DTD or fluoroethylene carbonate (FEC) in combination with another sulfur-containing additive, and and 3) propane-1-ene-1,3-sulfur in combination with DTD or another sulfur-containing additive. Based on a two-additive electrolyte system combined with a solvent and electrodes, including polyethersulfone (PES), These two additive electrolyte systems have the composition LNi x Mn y Co z O2 (generally It is abbreviated as NMC or NMCxyz, where x, y, and z are nickel, manganese, and It is made from lithium nickel manganese cobalt oxide with a molar ratio of 0.1 to 0.2. In certain embodiments, the positive electrode is NMC111, NMC532, In certain embodiments, the continuous crystalline structure is formed from NMC811 or NMC622. Single crystal macromolecules, resulting in electrodes with micrometer-sized regions of atoms (or particles). The NMC532 cathode formed with micrometer-side fine particles is due in part to the materials and processing conditions. The conditions result in larger particle sizes than are possible using conventional materials and processing conditions, making them particularly robust. It is shown to be.

[0214] Typical processing conditions are used to separate nanometer-sized particles into larger micrometer-sized aggregates. This results in an NMC electrode packed with zinc particles, forming nanometer-scale grain boundaries. Grain boundaries are defects that tend to degrade desirable properties (e.g., electrical properties). Therefore, it is usually desirable to reduce the number of particles and increase the particle size. This creates larger areas on the micrometer size scale, thereby enabling the The number of grain boundaries is reduced, improving electrical properties. The improved properties lead to a more robust battery system. In certain embodiments, larger domain sizes (micrometer size scale) Another NMC electrode may be processed to create a more robust system (e.g., a To create the stem, use NMC111, NMC811, NMC622, or another NM The C compound may be treated.

[0215] The positive electrode can be aluminum oxide (Al2O3), titanium dioxide (TiO2), or another The positive electrode may be coated with a material such as a coating. Coating the positive electrode may degrade the system. Reduces interfacial phenomena at the cathode, such as parasitic reactions, thermal abuse, or other phenomena that may cause The negative electrode may be made of natural graphite, artificial graphite, or another material. It may also be made from

[0216] The electrolyte is ethylene carbonate, ethyl methyl carbonate, methyl acetate, propylene Carbonate, dimethyl carbonate, diethyl carbonate, other carbonate solvents (cyclic or acyclic), another organic solvent, and / or another non-aqueous solvent. The solvent may be a lithium salt (such as LiPF6) dissolved in a combination of non-aqueous solvents. The solvent is present in higher concentrations than the additive, typically greater than 6% by weight. , which were produced using electrolyte solvents containing EC and EMC (with or without MA). These solvents are merely examples of other non-aqueous solvents, particularly other carbonate solvents. The systems tested to understand the effect of the addition of MA as an additive, electrode, and solvent were: EC and EMC solvents were used in the experiments to control the system. The electrolyte system is composed of propylene carbonate, ethylene carbonate, and dimethyl carbonate. carbonate, ethyl methyl carbonate, diethyl carbonate, other carbonate solvents (cyclic or other carbonates, including other organic solvents (cyclic or acyclic), other organic solvents, and / or other non-aqueous solvents. Solvents and / or other non-carbonate solvents may be used. The solvents may have a higher viscosity than the additives. It is present in low concentrations, usually above 6% by weight.

[0217] 2. In the additive mixture FEC and DTD, the concentration of FEC is preferentially 0.5 to 6 wt.%. and the concentration of DTD is preferentially between 0.25 and 5% by weight. For VC and DTD, the concentration of VC is preferentially between 0.5 and 6 wt.%, and that of DTD. The concentration is preferentially between 0.25 and 5% by weight.

[0218] Some of these new battery systems have improved charging and discharging rates, as well as the ability to charge and discharge rapidly. Energy storage and automotive applications (e.g., in electric vehicles) where lifetime during charging and discharging is important In particular, MA can be used in applications where the current rate is higher than the It can be used as an electrolyte solvent to extend the life when charged and discharged at room temperature. [Pre-experimental setup] The battery system itself may be packaged differently in accordance with the present disclosure, but experimental The setup typically uses a two-additive electrolyte system and positive and negative electrodes. To systematically evaluate battery systems containing specific materials and using typical setups All percentages mentioned within this disclosure are All percentages are by weight unless otherwise specified. The concentration employed will depend on the most desirable improved properties and the lithium This depends on other components and designs used within the ion battery and is separate from this disclosure. Those skilled in the art will understand that.

[0219] [Pouch Cell] The pouch cell used in the experimental setup contains 1M Li in a solvent with additives. Depending on the concentration of methyl acetate (0, 20, or 40%), the electrolyte (1) 1.2M in 30% ethylene carbonate and 70% ethyl methyl carbonate of LiPF6, (2) 24% ethylene carbonate, 56% ethyl methyl carbonate, and 1.2 M LiPF6 in 20% methyl acetate, or (3) 18% ethylene carbonate 1.2 M Li in 42% ethyl methyl carbonate, and 40% methyl acetate The electrolyte consists of 1M LiPF6 in PF6. The specified weight percentages The additive ingredients were added at this stage.

[0220] Pouch cells are NMC with micrometer-sized particles unless otherwise specified. The positive electrode is made of 532 (sometimes called single crystal NMC532) and the negative electrode is made of artificial graphite. To test a specific battery system, a standard NMC532 (having particles smaller than NMC, which has micrometer-sized particles) and NM Another positive electrode containing C622 was used, as well as a negative electrode (containing natural graphite).

[0221] Before electrolyte filling, the pouch cell was cut open under the heat seal to remove any residual water. The mixture was dried at 100°C under vacuum for 12 hours to obtain a granular solid. The cell was immediately transported to an argon-filled glove box for vacuum sealing and then filled with electrolyte. After filling, the cell was vacuum sealed.

[0222] After sealing, the pouch cell is placed in a temperature box at 40.0±0.1℃ and wetting is performed. The pouch cells were then subjected to a forming process. Unless otherwise specified, the formation process consisted of heating the pouch cell at 11mA (C / 20) for 4 The charge cycle consists of charging to 0.2V and discharging to 3.8V. C / x is the charge / discharge cycle that determines how much a cell will last at its initial capacity. , the time to charge or discharge the cell at the selected current is x hours. For example, C / 20 indicates that the charge or discharge takes 20 hours. The cell is then transported into a glove box and turned off to release any formed gases. The container was opened, re-vacuum sealed and the appropriate experiment performed.

[0223] [Electrochemical Impedance Spectroscopy] After storage and formation, electrochemical impedance spectroscopy (EIS) measurements were performed on the pouch cells. The cells were charged or discharged to 3.8 V, and then the temperature was measured at 10.0 ± 0.1°C. The temperature was measured at 10.0±0.1°C with a signal amplitude of 10mV and 100kHz. AC impedance spectrum from z to 10mHz with a resolution of 10 points per decade was collected.

[0224] LFO influence on impedance: In certain embodiments, the LFO is partially Two or three electrolyte additives are included in the system to reduce the impedance of the system. Figures 35A to 35D show the most common types of batteries used in most applications, such as LiPO2F2 (LFO, or FF). It has been shown that the addition of lithium fluoride reduces the cell impedance after formation. However, LFO is 2% PES + 1% DTD + 1% TTSPi (together PES21 When the cathode is mixed with NMC53, an increase in impedance is observed. 2, and the negative electrode is artificial graphite.

[0225] 35A-35D show the results of an electrolyte system with a positive electrode of NMC111 and a negative electrode of synthetic graphite. The experimental data for this system are summarized below. After formation, the pouch cells were measured at 10°C and 3.8V. The control electrolyte in Figures 35A to 35D was 30% ethylene carbonate. 1.0 M LiPF6 in ethyl methyl carbonate and 70% ethyl methyl carbonate. , in 30% ethylene carbonate and 70% ethyl methyl carbonate (control electrolyte) 1.0M LiPF6; 30% ethylene carbonate and 70% ethyl methyl carbonate 1.2M LiPF6 in electrolyte; control electrolyte + 1% LiPO2F2; control electrolyte + 2% LiPO2F2; and 20% methyl acetate + 1% LiPO2F2, impedance The experimental impedance is plotted against the real part of the impedance. The data are summarized in Figure 35B. %VC+1%LiPO2F2;20%MA+1%LiPO2F2+2%VC;PES21 1; and PES211 + 1% LiPO2F2, the real part of the impedance Summarize the experimental impedance data by plotting the negative of the imaginary part of the impedance. Figure 35C shows the results for the control electrolyte (same control as Figure 35A), 2% FEC, and 2% FEC + 1% For LiPO2F2; 1% DTD; and 1% DTD + 1% LiPO2F2, the impedance Plot the negative of the imaginary part of the impedance against the real part of the impedance to determine the experimental impedance. Figure 35D summarizes the data for control electrolyte (same control as Figure 35A); 30% 1.2M LiPF6 in ethylene carbonate and 70% ethyl methyl carbonate ;1%LiPO2F2;2%LiPO2F2;20%MA+1%LiPO2F2;2%V C;2%VC+1%LiPO2F2;20%MA+1%LiPO2F2+2%VC;PE S211;PES211+1%LiPO2F2;2%FEC, 2%FEC+1%LiPO Experimental impedance data for 2F2; 1% DTD; and 1% DTD + 1% LiPO2F2 This summarizes the data.

[0226] As can be seen in Figures 35A-35D, adding an LFO to most systems will improve the intrinsic However, when PES211 is present, adding LFO and the impedance increases.

[0227] Figure 36 shows the results of 1 in 30% ethylene carbonate and 70% ethyl methyl carbonate. 2%VC in 2M LiPF6 electrolyte solution; 1%LiPO2F2 + 2%VC; 1%L iPO2F2+2%FEC; and 1% LiPO2F2+1%VC+1%FEC additives This figure summarizes experimental EIS data for an electrolyte system containing ZnO at 3.8 V and 10 °C. The positive electrode was single crystal NMC532, and the negative electrode was synthetic graphite. be.

[0228] The LFO measured the impedance of the tested system with an NMC532 positive electrode and an artificial graphite negative electrode. The reason why the impedance did not decrease was because the cathode or This may be due to the large anode surface area. However, the LFO also has a low impedance. Therefore, adding an LFO does not decrease the impedance. , or neutral.

[0229] [Ultra-high precision cycling and storage experiments] To study the effectiveness of the disclosed battery system, including effective electrolyte additives and electrodes. Ultra-high precision cycling (UHPC) was performed. Standard UHPC procedures generate data To do this, use a current corresponding to C / 20 for 15 cycles, measuring 2.8 to 4.0 at 40°C. This involves cycling the cell between 0.5V and 3V. For coulombic efficiency, an accuracy of up to 30 ppm is achieved. To measure coulombic efficiency, end-of-charge capacity, slip, and other parameters, HC is employed. Details of the UHPC procedure are incorporated herein by reference in their entirety. TM Bond, JC Burns, DA Stevens, HMDah n,and JRDahn,Journal of the Electroche This is described in Medical Society, 160, A521 (2013).

[0230] Metrics measured and / or determined from UHPC measurements of particular interest include: Includes coulombic efficiency, normalized coulombic inefficiency, normalized end-of-charge capacity slip, and normalized discharge capacity quantity (or fade rate), and delta V. Coulombic efficiency is the discharge capacity (Q d ) to the previous Cycle charge capacity (Q c ) which is what is happening in a Li-ion cell. It tracks the parasitic reactions that occur during charging and includes contributions from both the positive and negative electrodes. This indicates that the deterioration of the electrolyte in the cell is minimal. The coulomb inefficiency per hour (CIE / h) is Normalized (per hour) coulomb inefficiency, where coulomb inefficiency is 1-CE This is defined as taking 1-CE and dividing by the time of the cycle in which CE was measured. The end-of-charge capacity movement (or slippage) is calculated by The bioreactions are tracked, as well as the mass loss of the positive material, if any. Normalized discharge capacity, or fade rate, is another important metric. A lower fade rate is desirable and typically indicates a longer-lasting battery system. Delta V is calculated as the difference between the average charging voltage and the average discharging voltage. The change in delta V is Closely related to polarization growth, the change in delta-V when cycling is small UHPC measurements allow tracking metrics with greater accuracy and precision This allows for the evaluation of various degradation mechanisms at a relatively fast rate, making it ideal for comparing electrolyte compositions. It is particularly suitable for

[0231] Two-electrolyte system with FEC or VC as additive: In certain embodiments, A two-additive electrolyte system with additive concentrations of approximately 0.25-6% forms part of the battery system. The battery system also includes NMC111, NMC532, NMC811, and NMC622 , or a positive electrode made from another NMC composition (NMCxyz). In some cases, the processing conditions produced larger particle sizes than those produced under normal processing conditions. Therefore, the cathode made from NMC532, which has micrometer-scale particles, is particularly It was shown to be robust.

[0232] Typical processing conditions are used to separate nanometer-sized particles into larger micrometer-sized aggregates. This results in an MC electrode packed with zinc particles, forming nanometer-scale grain boundaries. Grain boundaries are defects that tend to degrade desirable properties (e.g., electrical properties). Therefore, it is usually desirable to reduce the number of particles and increase the particle size. , creating larger areas, on the micrometer size scale, and thereby NMC electrodes This reduces the number of grain boundaries within the battery, improving its electrical properties. The improved properties lead to a more robust battery system. In certain embodiments, larger domain sizes (micrometer-sized domains) are obtained. Another NMC electrode may be processed to create a more robust To create a suitable system, use the NMC111, NMC811, NMC622, or another The NMC compound may be treated.

[0233] The positive electrode can be aluminum oxide (Al2O3), titanium dioxide (TiO2), or another 4A to 4J show the structure of a single crystal NMC532. A positive electrode made of 30% ethylene carbonate and a negative electrode made of artificial graphite were used. In a base electrolyte system containing 1.2 M LiPF6 in 0% ethyl methyl carbonate The novel two-additive electrolyte systems (VC+DTD and FEC+DTD) and the single-additive electrolyte Representative of the two additive systems of the present disclosure collected during a UHPC experiment comparing the solubility systems. 4A to 4J show typical experimental data. Specifically, the electrolyte system containing VC or FEC 1 illustrates the advantage of the two-additive system of the present disclosure, adding DTD to the stem.

[0234] Figure 4A shows the electrolyte systems containing 1% DTD, 2% VC, and 2% VC + 1% DTD. Figure 4B shows the time-normalized coulombic inefficiency per hour (CIE / h) versus cycle number. The results are shown for the couplants containing 1% DTD, 2% VC, and 2% VC + 1% DTD electrolyte systems. Figure 4C shows the CE versus cycle number for 1% DTD, 2% VC, and 2% V. End-of-charge values ​​plotted against cycle number for electrolyte systems containing C+1% DTD. Figure 4D shows the capacitance of the electrolytes containing 1% DTD, 2% VC, and 2% VC + 1% DTD. Figure 4E shows the discharge capacity versus cycle number for the 1% DTD, 2% VC, and Difference between average charge voltage and average discharge voltage for electrolyte system containing 2%VC+1%DTD vs. Figure 4F shows the number of cycles for 1% DTD, 2% FEC, and 2% FEC + 1% DTD. Time-normalized coulomb inefficiency per hour (CIE / h) vs. cycle Figure 4G shows the number of samples containing 1% DTD, 2% FEC, and 2% FEC + 1% DTD. Figure 4H shows the coulombic efficiency (CE) versus cycle number for the electrolyte system. For the number of cycles for electrolyte systems containing 2% FEC and 2% FEC + 1% DTD Figure 4I shows the end-of-charge capacity plotted at 1% DTD, 2% FEC, and 2% FEC. Figure 4J shows the discharge capacity versus cycle number for the electrolyte system containing % FEC + 1% DTD. , 1% DTD, 2% FEC, and 2% FEC + 1% DTD electrolyte systems. The difference between the average charge voltage and the average discharge voltage is shown versus the number of cycles.

[0235] 4A to 4J show the results of the VC+DTD and FEC+DTD-containing polymers. Experimental data show the benefits of using an electrolyte containing 30% ethylene carbonate and 70% ethylene carbonate by weight. In a base electrolyte system containing 1.2 M LiPF6 in ethyl methyl carbonate When DTD was added to an electrolyte system containing VC or FEC, the This shows that the performance of electrolyte systems containing the additive improves. Figures 4A-4J show that the two additive systems (VC+DTD and FEC+DTD) Higher CE (in-cell) compared to systems with no additive or only one additive lower electrolyte degradation at the positive electrode) and lower end-of-charge kinetics (lower electrolyte degradation at the positive electrode) ) . Furthermore, Figures 4A-4J show that the desired low fade rate (Q d ) are also shown. Therefore, the two additives (VC+DTD and / or FEC+DT D) Electrolyte systems with only one additive of DTD, VC, or FEC performs better (in terms of CIE / h, CE, end-of-charge slippage) than electrolyte systems containing do.

[0236] Figure 5 summarizes the last three cycles of data generated during the experiment shown in Figures 4A-4J. Figure 5A shows the results for 1% DTD, 2% FEC, 2% FEC + 1% DTD, 2% VC, and time-normalized coulombs per hour for electrolyte systems containing 2%VC+1%DTD Figure 5B shows a summary of the last three cycles of inefficiency (CIE / h). Electrolyte systems containing EC, 2% FEC + 1% DTD, 2% VC, and 2% VC + 1% DTD Figure 5C shows a summary of the last three cycles of fragment sliding per hour for the stem. TD, 2%FEC, 2%FEC+1%DTD, 2%VC, and 2%VC+1%DTD , showing a summary of the last three cycles of hourly fragment fades.

[0237] 5A to 5C show that the VC+DTD and electrolyte systems containing VC+DTD are Systems containing only additional additives, i.e., 2% FEC, 2% VC, or 1% DTD. Comparatively, lower normalized coulombic inefficiency (CIE / h) and lower fractions per hour slippage, which means these electrolyte systems have a longer lifespan. 5A and 5B show that 1% DTD without any other additives has the highest However, the DTD does not show VC or When combined with FEC, the two additives formed a synergistic effect that was not previously predicted. The two-additive electrolyte system showed improved CIE / h and Figure 5C shows the results of the VC and FEC additives as single additives or in combination with VC or FEC. As part of a two-additive electrolyte system, the presence of 1% DTD reduces fragment fractions per hour. This indicates that DTD can extend the life of the battery system of the present invention. In addition to DTD, other sulfur-containing compounds works similarly and can extend battery life.

[0238] Methyl acetate as electrolyte solvent: In certain embodiments, higher charging in addition to other properties and discharge rate is expected, to improve the battery system life. Methyl acetate (in concentrations up to 60%) is used for vehicles and other applications. 9A to 9I show that the electrolyte conductivity can be increased without significantly sacrificing the lifetime. In electrolyte systems containing VC or FEC with DTD to reduce viscosity, Typical data collected during some ultra-precise charging experiments demonstrating the ability to add methyl acetate. Data shows that the improved conductivity and reduced viscosity are beneficial for certain applications requiring higher charging rates. is important to

[0239] Figure 9A shows the results of 1 in 30% ethylene carbonate and 70% ethyl methyl carbonate. 2% FEC in a base electrolyte of 2M LiPF6; 30% ethylene carbonate and 2% FE in a base electrolyte of 1.2M LiPF6 in 70% ethyl methyl carbonate C+1% DTD; 24% ethylene carbonate, 56% ethyl methyl carbonate, and and 2% FEC in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18% ethylene 1.2 in 42% ethyl methyl carbonate, and 40% methyl acetate 2% FEC in a base electrolyte of LiPF6 at M; and 18% ethylene carbonate, 1.2M LiPF6 in 42% ethyl methyl carbonate and 40% methyl acetate Coulombic efficiency (CE) of the electrolyte system containing 2% FEC + 1% DTD in the base electrolyte ) versus cycle number.

[0240] Figure 9B shows the results of 1 in 30% ethylene carbonate and 70% ethyl methyl carbonate. 2% FEC in a base electrolyte of 2M LiPF6; 30% ethylene carbonate and 2% FE in a base electrolyte of 1.2M LiPF6 in 70% ethyl methyl carbonate C+1% DTD; 24% ethylene carbonate, 56% ethyl methyl carbonate, and and 2% FEC in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18% ethylene 1.2 in 42% ethyl methyl carbonate, and 40% methyl acetate 2% FEC in a base electrolyte of LiPF6 at M; and 18% ethylene carbonate, 1.2M LiPF6 in 42% ethyl methyl carbonate and 40% methyl acetate The number of cycles for the electrolyte system containing 2% FEC + 1% DTD in the base electrolyte was measured. Indicates the capacity of the plotted end-of-charge point.

[0241] Figure 9C shows the results of 1 in 30% ethylene carbonate and 70% ethyl methyl carbonate. 2% FEC in a base electrolyte of 2M LiPF6; 30% ethylene carbonate and 2% FE in a base electrolyte of 1.2M LiPF6 in 70% ethyl methyl carbonate C+1% DTD; 24% ethylene carbonate, 56% ethyl methyl carbonate, and and 2% FEC in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18% ethylene 1.2 in 42% ethyl methyl carbonate, and 40% methyl acetate 2% FEC in a base electrolyte of LiPF6 at M; and 18% ethylene carbonate, 1.2M LiPF6 in 42% ethyl methyl carbonate and 40% methyl acetate Discharge capacity vs. cycles for electrolyte systems containing 2% FEC + 1% DTD in base electrolyte Indicates a number.

[0242] Figure 9D shows the results of 1 in 30% ethylene carbonate and 70% ethyl methyl carbonate. 2% FEC in a base electrolyte of 2M LiPF6; 30% ethylene carbonate and 2% FE in a base electrolyte of 1.2M LiPF6 in 70% ethyl methyl carbonate C+1% DTD; 24% ethylene carbonate, 56% ethyl methyl carbonate, and and 2% FEC in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18% ethylene 1.2 in 42% ethyl methyl carbonate, and 40% methyl acetate 2% FEC in a base electrolyte of LiPF6 at M; and 18% ethylene carbonate, 1.2M LiPF6 in 42% ethyl methyl carbonate and 40% methyl acetate The average charging voltage and average The difference in discharge voltage versus the number of cycles is shown.

[0243] Figure 9F shows the results of 1 in 30% ethylene carbonate and 70% ethyl methyl carbonate. 2% VC in a base electrolyte of 2M LiPF6; 30% ethylene carbonate and 7 2% VC+ in a base electrolyte of 1.2M LiPF6 in 0% ethyl methyl carbonate 1% DTD; 24% ethylene carbonate, 56% ethyl methyl carbonate, and 2 2% VC in a base electrolyte of 1.2M LiPF6 in 0% methyl acetate; 24% ethylene in ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate 2%VC + 1%DTD in 1.2M LiPF6 base electrolyte; 18% ethylene carbonate 1.2M Li in 42% ethyl methyl carbonate, and 40% methyl acetate 2% VC in the base electrolyte of PF6; and 18% ethylene carbonate, 42% ethylene Base electrolysis of 1.2M LiPF6 in methyl methyl carbonate and 40% methyl acetate Coulombic efficiency (CE) versus cycle for electrolyte systems containing 2% VC + 1% DTD in the electrolyte Indicates a number.

[0244] Figure 9G shows the results of 1 in 30% ethylene carbonate and 70% ethyl methyl carbonate. 2% VC in a base electrolyte of 2M LiPF6; 30% ethylene carbonate and 7 2% VC+ in a base electrolyte of 1.2M LiPF6 in 0% ethyl methyl carbonate 1% DTD; 24% ethylene carbonate, 56% ethyl methyl carbonate, and 2 2% VC in a base electrolyte of 1.2M LiPF6 in 0% methyl acetate; 24% ethylene in ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate 2%VC + 1%DTD in 1.2M LiPF6 base electrolyte; 18% ethylene carbonate 1.2M Li in 42% ethyl methyl carbonate, and 40% methyl acetate 2% VC in the base electrolyte of PF6; and 18% ethylene carbonate, 42% ethylene Base electrolysis of 1.2M LiPF6 in methyl methyl carbonate and 40% methyl acetate Plotted against cycle number for an electrolyte system containing 2% VC + 1% DTD in the matrix. Indicates the end point of charging.

[0245] Figure 9H shows the results of 1 in 30% ethylene carbonate and 70% ethyl methyl carbonate. 2% VC in a base electrolyte of 2M LiPF6; 30% ethylene carbonate and 7 2% VC+ in a base electrolyte of 1.2M LiPF6 in 0% ethyl methyl carbonate 1% DTD; 24% ethylene carbonate, 56% ethyl methyl carbonate, and 2 2% VC in a base electrolyte of 1.2M LiPF6 in 0% methyl acetate; 24% ethylene in ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate 2%VC + 1%DTD in 1.2M LiPF6 base electrolyte; 18% ethylene carbonate 1.2M Li in 42% ethyl methyl carbonate, and 40% methyl acetate 2% VC in the base electrolyte of PF6; and 18% ethylene carbonate, 42% ethylene Base electrolysis of 1.2M LiPF6 in methyl methyl carbonate and 40% methyl acetate Figure 1 shows the discharge capacity versus cycle number for an electrolyte system containing 2% VC + 1% DTD in the electrolyte.

[0246] Figure 9I shows the results of 1 in 30% ethylene carbonate and 70% ethyl methyl carbonate. 2% VC in a base electrolyte of 2M LiPF6; 30% ethylene carbonate and 7 2% VC+ in a base electrolyte of 1.2M LiPF6 in 0% ethyl methyl carbonate 1% DTD; 24% ethylene carbonate, 56% ethyl methyl carbonate, and 2 2% VC in a base electrolyte of 1.2M LiPF6 in 0% methyl acetate; 24% ethylene in ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate 2%VC + 1%DTD in 1.2M LiPF6 base electrolyte; 18% ethylene carbonate 1.2M Li in 42% ethyl methyl carbonate, and 40% methyl acetate 2% VC in the base electrolyte of PF6; and 18% ethylene carbonate, 42% ethylene Base electrolysis of 1.2M LiPF6 in methyl methyl carbonate and 40% methyl acetate The average charge voltage and average discharge voltage of the electrolyte system containing 2% VC + 1% DTD in the electrolyte were The difference versus cycle number is shown.

[0247] 9A to 9I show the results of the analysis of the electrolyte solvent in a system containing both VC and FEC. This indicates that the addition of MA does not significantly compromise the overall performance of the battery system. , which, as the long-term cycling and plating experiments described later show, In particular, the performance of the two-additive electrolyte system of the present disclosure is enhanced by the addition of 10A to 10C show the results of the experiments shown in FIGS. 9A to 9I. The average of the last three cycles of data generated during the experiment is shown in Figures 10A-10C. The addition of MA as a polymer solvent did not affect the performance of the battery system of the present disclosure, which includes a two-additive electrolyte system. This proves that overall performance is not significantly compromised.

[0248] LFO as an additive: Figures 39A-39H and 40A-40H show the control electrolyte The LFO is used to improve overall system performance compared to the The paper summarizes the results of UHPC experiments, which show that the proposed method works well for

[0249] 37A-37F and 38A-38F show the results of the LFO-free control compared to the control without the LFO. Experimental storage data for different electrolyte systems containing LFO are summarized.

[0250] Figures 37A-37F show that LFO dramatically improves storage when no other additives are present. When LFO is added, the voltage drop is dramatically reduced after storage, and gas generation is Dramatically reduces noise and impedance. LFO is effective even in the presence of MA. 38A-38F show the results when LFO is added to an EC / DMC-based electrolyte. Similar results are shown when a good additive package such as 1% FEC + 1% DTD is used. However, once the DTD-based The electrolyte system changes color over time when mixed and stored in a glove box. It is possible that they may be excluded in the future.

[0251] Figures 46A-46D show the results of cell storage experiments, showing that more complex electrolytes improve storage performance. It shows comparable performance to 2%FEC+1%DTD in terms of performance.

[0252] 52A to 52D, 53A to 53D, 54A to 54D, and 55A to 55D. 55C also contains an additional electrolyte system containing LFO and 2%VC + 1%DTD for comparison purposes. As can be seen, the electrolyte system with LFO exhibited a 2% V C+1% shows performance equal to or better than the DTD system. The results of additional experiments on fragment fade and fragment sliding are shown below. 2% VC + 1% DTD electrolyte The system works very well: 1% LFO + 2% VC and 1% LFO + 1% VC. The +1% FEC electrolyte system also exhibits a significant increase in ionic strength (although not as much as the 2% VC + 1% DTD system). ) works well. This experimental data is consistent with the TAM experimental data.

[0253] Figure 57 shows the effect of UHPC cycling on impedance. The system performs well overall. Figures 58A-58D show two Electrolytes containing LFO with positive electrodes made from NMC622 with different coatings The experimental data for the electrolyte systems are summarized. In the different electrolyte systems studied, LFO , which also affects the voltage drop and impedance reduction of the system.

[0254] LFO is Guangzhou Tinci Materials Technolo gy Co., Ltd. and Shenzhen Capchem Technology It may be acquired from multiple sources, including the supplier, y Co., Ltd. The reaction rate is similar in the presence of air for at least 50 minutes, regardless of the Figure 61 shows the thermogravimetric analysis performed in an argon environment with a temperature gradient of 5°C / min. Through TGA experiments, mass loss is shown to be similar.

[0255] [Long-term cycling] The lifespan of a battery system is an important characteristic of the battery system. The charge and discharge rates are Long-term cycling experiments are performed under expected operating conditions. This helps determine the resilience of the battery system over time and ensures that it has sufficient life for the desired application. It is important to select a battery system that is compatible with the battery.

[0256] Embodiments of the present disclosure provide desirable long-term storage for different applications, including grid and vehicle storage. Specifically, MA was used as a solvent at concentrations up to 60%. The two additive electrolyte systems, VC+DTD and FEC+DTD, are used to improve charging speed and For automotive applications (especially energy storage in electric vehicles) where discharge rates are typically higher than for grid storage applications. This is particularly relevant to the storage of energy.

[0257] In long-term cycling experiments, the positive electrode was typically single-crystal N (unless otherwise specified). MC532 was used, and artificial graphite was used as the negative electrode (unless otherwise specified). Before the ignition experiment, the pouch cell was subjected to a formation process. First, the cell was charged at 11 mA (C The cell was charged to 4.2 V and discharged to 3.8 V using a 20 V AC / 200 V AC adapter. The container was transported and removed, cut open to release evolved gases, and then vacuum sealed again. After formation, the cells were cycled in a Neware charging system at 40°C ± 0.2°C or 20 The cell was housed in a temperature-controlled box at 10°C ± 0.2°C. The current was maintained at 1000 kJ / s until it dropped below C / 20. At the upper charge limit, a current of C / 3 (half a cycle of 3 hours) and a constant voltage step of 3.0V The cells were cycled between 0.05V and the upper charge limit (4.2V or 4.3V). Every 50 cycles Next, the cell was subjected to one complete cycle at C / 20.

[0258] Two-electrolyte system with FEC or VC as additive: In certain embodiments, A two-additive electrolyte system with additive concentrations of approximately 0.25-6% forms part of the battery system. 6A to 6F show long-term results at 40°C and a C / 3 constant charge, constant voltage (CCCV) charge rate. Figures 6A-6F show typical experimental data from a cycling study. The use of additive electrolyte systems, specifically electrolytes containing DTDs with VC or FEC Figure 6A shows a 1% DTD, 2% FE test cycled between 3.0 V and 4.2 V. C, electrolyte systems containing 2% FEC + 1% DTD, 2% VC, and 2% VC + 1% DTD Figure 6B shows experimental data for the capacity versus cycle number of the system between 3.0 V and 4.2 V. Cycles: 1% DTD, 2% FEC, 2% FEC + 1% DTD, 2% VC, and 2 Experimental data for normalized capacity versus cycle number for an electrolyte system containing 1% VC + 1% DTD are shown. Figure 6C shows a 1% DTD, 2% FEC, 2 %FEC+1%DTD, 2%VC, and 2%VC+1%DTD electrolyte systems , experimental data of voltage hysteresis (difference between average charge voltage and average discharge voltage) vs. cycle number Figure 6D shows the results of a 1% DTD, 2% FEC, Electrolyte systems containing 2% FEC + 1% DTD, 2% VC, and 2% VC + 1% DTD Figure 6E shows experimental data for the capacity versus cycle number of the 1000-mAh battery. 1% DTD, 2% FEC, 2% FEC + 1% DTD, 2% VC, and 2% V 1 shows experimental data for normalized capacity versus cycle number for electrolyte systems containing C+1% DTD. Figure 6F shows a 1% DTD, 2% FEC, 2% F cycled between 3.0 V and 4.2 V. The electrochemical properties of the electrolyte systems containing EC+1% DTD, 2% VC, and 2% VC+1% DTD were Experimental data for pressure hysteresis versus number of cycles are shown. Experimental data are for single VC or FEC. Compared with the single-additive electrolyte system, the two-additive electrolyte system (DTD+FEC and D TD+VC) has a lower capacity loss when cycled to 4.2 or 4.3V, It shows that the ZnO layer experiences lower polarization growth.

[0259] 7A-7F show typical results of long-term cycling at 20°C and a C / 3 CCCV charge rate. 6A-6F, Figs. 7A-7F show experimental data. Figures 7A-7F show the benefits of including DTD as an additive in electrolyte systems containing 4 This confirms that the benefits seen at 0°C are still seen at lower temperatures, in this case 20°C. Figure 7A shows a 1% DTD, 2% F cycled between 3.0 V and 4.3 V. Electrolyte systems containing EC, 2% FEC + 1% DTD, 2% VC, and 2% VC + 1% DTD Figure 7B shows experimental data of capacity versus cycle number for the stem. Cycle through: 1% DTD, 2% FEC, 2% FEC + 1% DTD, 2% VC, and Experimental data for normalized capacity versus cycle number for electrolyte systems containing 2% VC + 1% DTD are shown. Figure 7C shows the results of a 1% DTD, 2% FEC, Electrolyte systems containing 2% FEC + 1% DTD, 2% VC, and 2% VC + 1% DTD Experimental data of voltage hysteresis (difference between average charge voltage and average discharge voltage) vs. cycle number Figure 7D shows a 1% DTD, 2% FEC battery cycled between 3.0 V and 4.3 V. , 2% FEC + 1% DTD, 2% VC, and 2% VC + 1% DTD. Figure 7E shows experimental data for the capacity versus cycle number of the sample between 3.0 V and 4.3 V. Cycle, 1% DTD, 2% FEC, 2% FEC+1% DTD, 2% VC, and 2% Experimental data showing normalized capacity versus cycle number for electrolyte systems containing VC + 1% DTD are shown. Figure 7F shows the results of a 1% DTD, 2% FEC, 2% of electrolyte systems containing FEC + 1% DTD, 2% VC, and 2% VC + 1% DTD. Experimental data on voltage hysteresis (difference between average charge voltage and average discharge voltage) versus cycle number are shown. Figures 7A through 7F show the effect of VC or This confirms the benefits of including DTD in an electrolyte with FEC.

[0260] Figures 6A to 6F show the two-additive electrolyte system consisting of DTD+VC or DTD+FEC. Figures 6A-6F show the advantages of using VC or F as part of a two-additive electrolyte system. By cycling at 40°C with a DTD containing EC, 7A-7F show that the capacitance loss is reduced and the polarization growth is reduced. Figures 7A-7F show the benefits of DTD when cycling long-term at 20°C. Cycle at 20°C containing DTD with VC or FEC as part of the electrolyte system This reduces the capacitance loss at 4.2V (slightly) and 4.3V (more significantly). Therefore, at both 20°C and 40°C, the VC and 2. Additive system containing DTD with FEC reduces capacity loss and reduces polarization growth This improves the battery system.

[0261] In certain embodiments, the positive electrode is selected from the group consisting of NMC111, NMC532, NMC822, NMC6 22, and / or NMCxyz. In particular, the particle size of NMC532 is larger than the grain size of other standard MC materials, which are more polycrystalline and have smaller grain sizes. Therefore, cathodes made from single-crystal NMC532 have been shown to be particularly robust. 8A-8I illustrate specific embodiments of the present disclosure that include a positive electrode formed from single crystal NMC532. Figure 8A shows typical empirical data collected during cycling experiments of electrolyte compositions according to 3. 1.2M LiP in 0% ethylene carbonate and 70% ethyl methyl carbonate Cycled between 3.0V and 4.3V at 40°C in F6 base electrolyte, 2% FE C, 1%FEC+1%DTD, 2%FEC+1%DTD, 1%FEC+1%MMDS, and Peak capacity versus cycle number experiments for electrolyte systems containing 2% FEC and 1% MMDS Figure 8B shows the data for 30% ethylene carbonate and 70% ethyl methyl carbonate. In a base electrolyte of 1.2 M LiPF6 in ammonium nitrate, the voltage ranges from 3.0 V to 4.3 V at 40 °C. Cycles between 2%FEC, 1%FEC+1%DTD, 2%FEC+1%DTD, 1 %FEC + 1%MMDS, and 2%FEC + 1%MMDS electrolyte systems Figure 8C shows experimental data for normalized capacity versus cycle number for 30% ethylene carbonate and In a base electrolyte of 1.2 M LiPF6 in 70% ethyl methyl carbonate, Cycle between 3.0V and 4.3V at °C, 2% FEC, 1% FEC + 1% DTD, 2%FEC+1%DTD, 1%FEC+1%MMDS, and 2%FEC+1%MMDS Voltage hysteresis (difference between average charge voltage and average discharge voltage) vs. Figure 8D shows experimental data for cycle counts. 3.0 V at 40 °C in a base electrolyte of 1.2 M LiPF6 in methyl carbonate. to 4.3V, 2%VC, 1%VC+1%DTD, 2%VC+1%D Electrolyte systems containing TD, 1%VC+1%MMDS, and 2%VC+1%MMDS , and experimental data for peak capacity versus cycle number. and in a base electrolyte of 1.2 M LiPF6 in 70% ethyl methyl carbonate. Cycling between 3.0V and 4.3V at 40°C, 2%VC, 1%VC+1%DTD, Includes 2%VC+1%DTD, 1%VC+1%MMDS, and 2%VC+1%MMDS Figure 8F shows experimental data for the normalized capacity versus cycle number of the electrolyte system. 1.2M LiP in 0% ethylene carbonate and 70% ethyl methyl carbonate Cycled between 3.0V and 4.3V at 40°C in F6 base electrolyte, 2% FE C, 1%VC+1%DTD, 2%VC+1%DTD, 1%VC+1%MMDS, and 2 Voltage hysteresis (average charging voltage vs. average voltage) for electrolyte systems containing %VC+1%MMDS Figure 8G shows experimental data for the 30% ethylene carbonate (30%) vs. cycle number. In a base electrolyte of 1.2M LiPF6 in ethyl methyl carbonate and 70% ethyl methyl carbonate Cycle between 3.0V and 4.3V at 40℃, 2%PES, 1%PES+1% DTD, 2%PES+1%DTD, 1%PES+1%MMDS, and 2%PES+1% Figure 8H shows experimental data for peak capacity versus cycle number for an electrolyte system containing MMDS. is a 1.2M solution in 30% ethylene carbonate and 70% ethyl methyl carbonate. Cycle between 3.0 V and 4.3 V at 40 °C in a LiPF6-based electrolyte. %PES, 1%PES+1%DTD, 2%PES+1%DTD, 1%PES+1%MMD Normalized capacity versus cycle number for electrolyte systems containing S and 2% PES + 1% MMDS Figure 8I shows the experimental data for 30% ethylene carbonate and 70% ethyl methyl acrylate. In a base electrolyte of 1.2 M LiPF6 in carbonate, the voltage ranges from 3.0 V to 4.0 V at 40 °C. Cycle between 3V, 2%FEC, 1%PES+1%DTD, 2%PES+1%DT D, electrolyte systems containing 1% PES + 1% MMDS, and 2% PES + 1% MMDS The experimental data for voltage hysteresis (the difference between the average charge voltage and the average discharge voltage) are shown in Figure 8. Figures 8A-8I show the results of NMC532 with 1% VC, 2% VC, 1% FEC, or 2% FEC. The results show that a two-additive electrolyte system with 1% DTD works well. DTD performed better as an additive with VC or FEC than MMDS.

[0262] Methyl acetate as electrolyte solvent: In certain embodiments, methyl acetate is present in an amount of up to (by weight) Concentrations up to 60% are generally ethylene carbonate and / or ethyl methyl carbonate. In combination with cellulose, it is used as an electrolyte solvent. Figure 16F shows the results of experiments conducted at 20°C and 40°C, respectively. The cells with MA as the solvent performed better than the cells without DTD.

[0263] Figure 15A shows the results of a 30% ethylene carbonate and 70% ethylene carbonate battery cycled up to 4.2V. 2% FEC in a base electrolyte of 1.2 M LiPF6 in ethyl methyl carbonate; 1.2M Li in 30% ethylene carbonate and 70% ethyl methyl carbonate 1% FEC + 1% DTD in base electrolyte of PF6; 24% ethylene carbonate, 56 1.2M LiPF6 in 20% ethyl methyl carbonate and 20% methyl acetate 2% FEC in electrolyte; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate Carbonate, and 2% in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate FEC+1%DTD; 18% ethylene carbonate, 42% ethyl methyl carbonate, and 2% FEC in a base electrolyte of 1.2 M LiPF6 in 40% methyl acetate; and 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% acetic acid Electrolysis of 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in methyl 1 is a plot of experimental data obtained at 20° C. of capacity versus cycle number for a quality system.

[0264] Figure 15B shows the results of a 30% ethylene carbonate and 70% ethylene carbonate battery cycled up to 4.2 V. 2% FEC in a base electrolyte of 1.2 M LiPF6 in ethyl methyl carbonate; 1.2M Li in 30% ethylene carbonate and 70% ethyl methyl carbonate 1% FEC + 1% DTD in base electrolyte of PF6; 24% ethylene carbonate, 56 1.2M LiPF6 in 20% ethyl methyl carbonate and 20% methyl acetate 2% FEC in electrolyte; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate Carbonate, and 2% in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate FEC+1%DTD; 18% ethylene carbonate, 42% ethyl methyl carbonate, and 2% FEC in a base electrolyte of 1.2 M LiPF6 in 40% methyl acetate; and 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% acetic acid Electrolysis of 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in methyl 1 is a plot of experimental data obtained at 20°C of normalized capacity versus cycle number for a 20°C system. do.

[0265] Figure 15C shows the results of a 30% ethylene carbonate and 70% ethylene carbonate battery cycled up to 4.2 V. 2% FEC in a base electrolyte of 1.2 M LiPF6 in ethyl methyl carbonate; 1.2M Li in 30% ethylene carbonate and 70% ethyl methyl carbonate 1% FEC + 1% DTD in base electrolyte of PF6; 24% ethylene carbonate, 56 1.2M LiPF6 in 20% ethyl methyl carbonate and 20% methyl acetate 2% FEC in electrolyte; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate Carbonate, and 2% in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate FEC+1%DTD; 18% ethylene carbonate, 42% ethyl methyl carbonate, and 2% FEC in a base electrolyte of 1.2 M LiPF6 in 40% methyl acetate; and 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% acetic acid Electrolysis of 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in methyl Voltage hysteresis (difference between average charge voltage and average discharge voltage) versus number of cycles for quality systems , is a plot of experimental data obtained at 20°C.

[0266] Figure 15D shows the results of a 30% ethylene carbonate and 70% ethylene carbonate battery cycled up to 4.3 V. 2% FEC in a base electrolyte of 1.2 M LiPF6 in ethyl methyl carbonate; 1.2M Li in 30% ethylene carbonate and 70% ethyl methyl carbonate 1% FEC + 1% DTD in base electrolyte of PF6; 24% ethylene carbonate, 56 1.2M LiPF6 in 20% ethyl methyl carbonate and 20% methyl acetate 2% FEC in electrolyte; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate Carbonate, and 2% in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate FEC+1%DTD; 18% ethylene carbonate, 42% ethyl methyl carbonate, and 2% FEC in a base electrolyte of 1.2 M LiPF6 in 40% methyl acetate; and 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% acetic acid Electrolysis of 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in methyl 1 is a plot of experimental data obtained at 20° C. of capacity versus cycle number for a quality system.

[0267] Figure 15E shows the results of a 30% ethylene carbonate and 70% ethylene carbonate battery cycled up to 4.3 V. 2% FEC in a base electrolyte of 1.2 M LiPF6 in ethyl methyl carbonate; 1.2M Li in 30% ethylene carbonate and 70% ethyl methyl carbonate 1% FEC + 1% DTD in base electrolyte of PF6; 24% ethylene carbonate, 56 1.2M LiPF6 in 20% ethyl methyl carbonate and 20% methyl acetate 2% FEC in electrolyte; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate Carbonate, and 2% in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate FEC+1%DTD; 18% ethylene carbonate, 42% ethyl methyl carbonate, and 2% FEC in a base electrolyte of 1.2 M LiPF6 in 40% methyl acetate; and 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% acetic acid Electrolysis of 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in methyl 1 is a plot of experimental data obtained at 20°C of normalized capacity versus cycle number for a 20°C PET system. do.

[0268] Figure 15F shows the results of a 30% ethylene carbonate and 70% ethylene carbonate cycled up to 4.3 V. 2% FEC in a base electrolyte of 1.2 M LiPF6 in ethyl methyl carbonate; 1.2M Li in 30% ethylene carbonate and 70% ethyl methyl carbonate 1% FEC + 1% DTD in base electrolyte of PF6; 24% ethylene carbonate, 56 1.2M LiPF6 in 20% ethyl methyl carbonate and 20% methyl acetate 2% FEC in electrolyte; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate Carbonate, and 2% in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate FEC+1%DTD; 18% ethylene carbonate, 42% ethyl methyl carbonate, and 2% FEC in a base electrolyte of 1.2 M LiPF6 in 40% methyl acetate; and 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% acetic acid Electrolysis of 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in methyl Voltage hysteresis (difference between average charge voltage and average discharge voltage) versus number of cycles for quality systems , is a plot of experimental data obtained at 20°C.

[0269] Figures 15A-15F show the results of the system containing FEC and the system using MA as a solvent at 20°C. This shows the importance of DTD in systems that use it. Cells with DTDs are especially important for MAs. In cells containing DTD, it performed better than cells without DTD. The 2%FEC+1%DTD exhibits very stable capacitance retention at 4.3V. Figures 16A-16F show the results of experiments conducted at 40°C. The cells with DTD Cells containing MA performed better than cells without DTD. Figure 16A shows that up to 4 30% ethylene carbonate and 70% ethyl methyl carbonate cycled to 0.2V 2% FEC in a base electrolyte of 1.2M LiPF6 in sulphate; 30% ethylene carbonate Base electrolyte of 1.2M LiPF6 in ethyl methyl carbonate and 70% ethyl methyl carbonate 1% FEC + 1% DTD; 24% ethylene carbonate, 56% ethyl methyl carbonate nate, and 2% FE in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate C; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate, and 2 2% FEC + 1% DTD in a base electrolyte of 1.2 M LiPF6 in 0% methyl acetate; 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate 2% FEC in a base electrolyte of 1.2M LiPF6 in a 18% ethylene carbonate solution; 1.2M in carbon dioxide, 42% ethyl methyl carbonate, and 40% methyl acetate Capacity vs. electrolyte system containing 2% FEC + 1% DTD in LiPF6 base electrolyte 1 is a plot of experimental data obtained at 40° C. versus cycle number.

[0270] Figure 16B shows the results of a 30% ethylene carbonate and 70% ethylene carbonate battery cycled up to 4.2 V. 2% FEC in a base electrolyte of 1.2 M LiPF6 in ethyl methyl carbonate; 1.2M Li in 30% ethylene carbonate and 70% ethyl methyl carbonate 1% FEC + 1% DTD in base electrolyte of PF6; 24% ethylene carbonate, 56 1.2M LiPF6 in 20% ethyl methyl carbonate and 20% methyl acetate 2% FEC in electrolyte; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate Carbonate, and 2% in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate FEC+1%DTD; 18% ethylene carbonate, 42% ethyl methyl carbonate, and 2% FEC in a base electrolyte of 1.2 M LiPF6 in 40% methyl acetate; and 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% acetic acid Electrolysis of 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in methyl 1 is a plot of experimental data obtained at 40°C of normalized capacity versus cycle number for a 40°C system. do.

[0271] Figure 16C shows the results of a 30% ethylene carbonate and 70% ethylene carbonate battery cycled up to 4.2 V. 2% FEC in a base electrolyte of 1.2 M LiPF6 in ethyl methyl carbonate; 1.2M Li in 30% ethylene carbonate and 70% ethyl methyl carbonate 1% FEC + 1% DTD in base electrolyte of PF6; 24% ethylene carbonate, 56 1.2M LiPF6 in 20% ethyl methyl carbonate and 20% methyl acetate 2% FEC in electrolyte; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate Carbonate, and 2% in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate FEC+1%DTD; 18% ethylene carbonate, 42% ethyl methyl carbonate, and 2% FEC in a base electrolyte of 1.2 M LiPF6 in 40% methyl acetate; and 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% acetic acid Electrolysis of 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in methyl Voltage hysteresis (difference between average charge voltage and average discharge voltage) versus number of cycles for quality systems , is a plot of experimental data obtained at 40°C.

[0272] Figure 16D shows the results of a 30% ethylene carbonate and 70% ethylene carbonate battery cycled up to 4.3 V. 2% FEC in a base electrolyte of 1.2 M LiPF6 in ethyl methyl carbonate; 1.2M Li in 30% ethylene carbonate and 70% ethyl methyl carbonate 1% FEC + 1% DTD in base electrolyte of PF6; 24% ethylene carbonate, 56 1.2M LiPF6 in 20% ethyl methyl carbonate and 20% methyl acetate 2% FEC in electrolyte; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate Carbonate, and 2% in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate FEC+1%DTD; 18% ethylene carbonate, 42% ethyl methyl carbonate, and 2% FEC in a base electrolyte of 1.2 M LiPF6 in 40% methyl acetate; and 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% acetic acid Electrolysis of 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in methyl 1 is a plot of experimental data obtained at 40° C. of capacity versus cycle number for a quality system.

[0273] Figure 16E shows the results of a 30% ethylene carbonate and 70% ethylene carbonate battery cycled up to 4.3 V. 2% FEC in a base electrolyte of 1.2 M LiPF6 in ethyl methyl carbonate; 1.2M Li in 30% ethylene carbonate and 70% ethyl methyl carbonate 1% FEC + 1% DTD in base electrolyte of PF6; 24% ethylene carbonate, 56 1.2M LiPF6 in 20% ethyl methyl carbonate and 20% methyl acetate 2% FEC in electrolyte; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate Carbonate, and 2% in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate FEC+1%DTD; 18% ethylene carbonate, 42% ethyl methyl carbonate, and 2% FEC in a base electrolyte of 1.2 M LiPF6 in 40% methyl acetate; and 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% acetic acid Electrolysis of 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in methyl 1 is a plot of experimental data obtained at 40°C of normalized capacity versus cycle number for a 40°C system. do.

[0274] Figure 16F shows the results of a 30% ethylene carbonate and 70% ethylene carbonate battery cycled up to 4.3 V. 2% FEC in a base electrolyte of 1.2 M LiPF6 in ethyl methyl carbonate; 1.2M Li in 30% ethylene carbonate and 70% ethyl methyl carbonate 1% FEC + 1% DTD in base electrolyte of PF6; 24% ethylene carbonate, 56 1.2M LiPF6 in 20% ethyl methyl carbonate and 20% methyl acetate 2% FEC in electrolyte; ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate Carbonate, and 2% in a base electrolyte of 1.2M LiPF6 in 20% methyl acetate FEC+1%DTD; 18% ethylene carbonate, 42% ethyl methyl carbonate, and 2% FEC in a base electrolyte of 1.2 M LiPF6 in 40% methyl acetate; and 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% acetic acid Electrolysis of 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in methyl Voltage hysteresis (difference between average charge voltage and average discharge voltage) versus number of cycles for quality systems , is a plot of experimental data obtained at 40°C.

[0275] Figures 16A-16F show the results of the system containing FEC and the system using MA as the solvent at 40°C. This shows the importance of DTDs in systems that use them. In general, cells with DTDs are The cells containing MA performed better than the cells without DTD. In the two-additive electrolyte system with 2% FEC + 1% DTD, the same Compared to the two-additive electrolyte system without MA, the effect of DTD is slightly weakened. Furthermore, the addition of up to 40% MA at 4.3 V reduces the cycle life. D and MA can have a symbiotic increase in the performance of the two additive electrolyte systems. However, this increase weakens when cycling up to 4.3V. In certain disclosed embodiments, the electrolyte system operates only up to 4.2V. In another embodiment shown, the electrolyte system operates up to 4.3 V but with less than 40% M This is the case for concentration A.

[0276] NMC622 as the cathode: In certain embodiments, the battery system is made from NMC622 In a particular embodiment, the positive electrode is made of aluminum oxide (Al2O3). , titanium dioxide (TiO2), or another coating. 17A to 17F show the results of the test with coated NMC622 as the positive electrode at 40°C and C / 3 CCCV. Experimental data for long-term cycling of additive or two-additive electrolyte systems are shown. The dashed lines indicate This is an estimate based on experimental data.

[0277] More specifically, Figure 17A shows the FEC and / or D FIG. 17 is a plot of experimental data of capacity versus cycle number for electrolyte systems containing TD. B, Electrolyte systems containing FEC and / or DTD cycled up to 4.3 V 17C is a plot of experimental data of normalized capacity versus cycle number for a 4.3V maximum. Voltage hysteresis of electrolyte systems containing FEC and / or DTD cycled to 1 is a plot of experimental data of voltage difference (the difference between the average charge voltage and the average discharge voltage) versus cycle number. Figure 17D shows the electrochemical properties of electrolyte systems containing VC and / or DTD cycled up to 4.3 V. Figure 17E shows experimental plots of capacity versus cycle number for a system. Normalized capacity vs. cycle of electrolyte systems containing VC and / or DTD cycled at 1000 kJ / s. Figure 17F shows experimental data plots of V and V cycled up to 4.3 V. Voltage hysteresis (average charging voltage vs. average discharging voltage) for electrolyte systems containing ZnO and / or DTD 1 is a plot of experimental data (difference between applied voltage and applied voltage) versus number of cycles.

[0278] 17A-17F show that even when different cathodes were selected, the experimental data were consistent with the two additive The electrolyte systems with the agents, i.e., VC+DTD and FEC+DTD, were better than those with the VC, It has been shown that FEC or DTD exhibit superior performance compared to either additive alone. This shows that:

[0279] Natural graphite as anode: In certain embodiments, the battery system is made from natural graphite. 18A to 18B and 19 show the results of the battery test at 40°C and C / 3 CCCV. Additional long-term tests were performed using single crystal NMC532 as the negative electrode and natural graphite as the negative electrode. Figure 18A shows data from a cycling experiment. Figure 18B shows the normalized capacity plotted against cycle number. Figure 19 shows , voltage hysteresis (difference between average charge voltage and average discharge voltage) versus cycle number. 18A to 18B and 19 show that the dual electrolyte additive system containing DTD+FEC exhibits the same properties as the additive Although the results show that the performance improves over electrolyte systems containing only FEC, 6-F, where a graphite anode was used, the performance of this particular synthetic graphite anode is This suggests that this particular graphite anode is superior to the natural graphite anode in the additive electrolyte system. is doing.

[0280] In a particular embodiment, the battery system has a natural graphite anode. Its use is significant as a cost saving measure over the normally more expensive synthetic graphite. Therefore, when cost is the main factor and some performance trade-offs can be made, Natural graphite can be a good choice.

[0281] LFO as an Additive: In certain embodiments, LFO is added to the electrolyte system. Figure 41A shows the Coulombic inefficiency of different electrolyte systems, including systems containing LFO. Figure 41B summarizes the data for the LFO-incorporated system vs. the upper cutoff voltage. This paper summarizes data on fraction fade versus upper cutoff voltage for different electrolyte systems. Figure 41C shows the end-of-charge capacity slip for different electrolyte systems, including systems containing LFO. Figure 42A summarizes the data versus upper cutoff voltage. Figure 42A shows an expanded view of Figure 41A. Coulombic inefficiency versus upper cutoff for different electrolyte systems, including systems with LFO Figure 42B shows an expanded view of 41B, and summarizes the voltage data. We summarize data on fraction fade versus upper cutoff voltage for different electrolyte systems, including Figure 42C shows an expanded view of 41C, showing different electrolytic systems, including systems with LFOs. The data summarizes the end-of-charge capacity slip versus upper cut-off voltage for the control system. Adding LFO to the mixture significantly improves the UHPC results. 1% LFO dramatically improves the situation compared to 0.5% LFO. CIE / h is the 1% LFO is about 4 x 10 -5 h -1 In comparison, 2% VC + 1% DT in the control The best electrolyte system without LFOs, such as D, is 3×10 -5 h -1 It is nearby.

[0282] 43A-43D show long-term results for different electrolyte systems, including systems containing LFO. The results of long-term cycling are summarized in Table 1. The results of long-term cycling show that the addition of LFO Dramatically improved impedance growth in tested systems, corroborating UHPC data In particular, the control electrolyte and the electrolyte system containing 20% ​​MA were compared at 1% L. Addition of FO improves long-term cycling and impedance.

[0283] [Microcalorimetry] Microcalorimetry measures the heat flow into the cell during operation. The heat flow into the cell is determined by three different effects: The results are (1) ohmic heating and (2) entropy change due to the Li inserted in the electrode. and (3) a combination of parasitic reactions (electrolyte with additives, degradation at either electrode). The test cells contain the same physical design, differing only in the electrolyte, so the difference in heat flow is This is mainly due to differences in parasitic heat flow. Nevertheless, Downie et al. ournal of the Electrochemical Society,16 1, A1782-A1787 (2014)) and Glazier et al. (Journal of the Electrochemical Society,164(4)A56 7-A573(2017)) to extract the parasitic heat flow from the total heat flow. Both of these references are incorporated herein in their entirety. Cells with lower parasitic heat flow during cycling have longer life. Measured as a function of cell voltage. By plotting the parasitic heat flow, the voltage dependence of the parasitic reaction rate can be observed. can be done.

[0284] Microcalorimetry procedure: Connect two cells of each electrolyte to a Maccor charger and heat to 40.0 °C. on a TAMIII microcalorimeter (TA Instruments, stability ±0.0001°C, The baseline drift during the experiment was greater than ±0.5 μW. All specifications and information regarding microcalorimetry calibration, cell connections, and operating procedures are available. Information can be found in previous publications (e.g., Downie et al., ECS Elec Trochemical Letters 2, A106-A109 (2013)). To ensure a stable SEI over time, the sensor is The battery was cycled four times and then tested to investigate the performance and parasitic heat flow at different voltage ranges. The cells were then charged at 1 mA between 4.0 V and different upper cutoff limits. Only one set of heat flow data is presented for each electrolyte since this resulted in a performance

[0285] The protocol for 1 mA cycling is as follows: 1. Charge to 4.2V, discharge to 4.0V 2. Charge to 4.3V, discharge to 4.0V (repeated) Charge to 3.4.4V, discharge to 4.0V (repeated) 6. Charge to 4.2V, discharge to 4.0V Additional experimental details are found in the Journal of of the Electrochemical Society,164(4)A56 7-A573(2017).

[0286] The experimental data shown in Figures 11 to 14 show that the positive electrode and A pouch cell having a negative electrode and an artificial graphite negative electrode was used. Excluding the additive, the electrolyte was: (1) 1.2M in 30% ethylene carbonate and 70% ethyl methyl carbonate LiPF6, (2) ethylene 24% ethylene carbonate, 56% ethyl methyl carbonate nate, and 1.2M LiPF6 in 20% methyl acetate, or (3) 18% ethyl acetate. 1.2 in 40% methyl carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate M LiPF6.

[0287] Figure 11 shows experimental data (parasitic heat flow vs. voltage) from a calorimetric experiment when charging to 4.2V. 12A and 12B show the experimental data of the calorimetric experiment when charged to 4.3 V. The data (parasitic heat flow vs. voltage) are shown. Since charging up to 4.3V was repeated, each plot is 1 13A and 13B show the results of charging up to 4.4 V. The experimental data (parasitic heat flow vs. voltage) is shown. Charging up to 4.4V was repeated, and each plot The plots show the results for one charge. The difference plots (Fig. 11, Fig. 12A, Fig. 12B, Fig. 1 3A and 13B) were taken to measure the heat flow of each electrolyte mixture and the control (2% FEC). The heat flow is calculated by subtracting the generated heat flow. Table 1 summarizes the data displayed in Figure 14 in tabular form. There are. [Table 1]

[0288] Figures 11 to 14 and Table 1 show that adding DTD to FEC results in lower parasitic heat flow ( 11 to 14 and Table 1 also show that the It was also shown that adding MA resulted in a higher parasitic heat flow (higher parasitic reaction rate). However, this increase may be mitigated by DTD, which may result in a decrease in the This helps reduce the increase in parasitic reaction rates from

[0289] LFO as an additive: Figure 47 shows that the charge heat flow is affected by the parasitic heat flow, charge overpotential, and discharge overpotential. Figures 48a to 48F show the results of the TAM experiment. The plots compare the system with 2%VC + 1%DTD. Figures 48a-48F show , which shows that 2%VC+1DTD is better than 2%FEC+1DTD. They also offer a 1% over 4.3V output when optimized for an LFO in your system. It also shows that LFO+1%VC+1%FEC is superior to 2%VC+1%DTD. Compared to a system with 1% LFO, 1% LFO + 1% VC is It exhibits performance almost equivalent to 0+1%VC+1%FEC, and 2%VC+1% at 4.3V. As can be seen in Figures 50A-50C, the optimal LFO composition is approximately 1.0%. Figure 51 shows the average parasitic heat as a function of cycles for the best performing cell. A 0.5% LFO with 1% VC + 1% FEC shows the current after 4.4V cycles. 2%VC+1%LFO is not the same as 2%VC+1%DTD. Always comparable. Therefore, systems with VC and with or without DTD is possible.

[0290] [Plating experiment] The plating experiment will test the vehicle's ability to charge at high speeds. Very important in energy storage, but slower charging in grid storage The rate can be acceptable. High-speed charging is limited primarily by lithium plating on the negative electrode. This leads to safety issues and reduces cycle and calendar life. Therefore, an electrolyte system that allows for higher charging rates without plating is advantageous. To study the effect of lithium plating, a plating experiment was conducted. Indicates a lot.

[0291] To test the charging capability of the cell, a plating experiment was carried out. After EIS measurements, 1C, 1V between 2.8 and 4.1V using Maccor charging system at ±0.1°C The cells were charged and discharged at constant current (C-rate) of 0.5C and 2.0C to ensure reproducibility. To ensure the active lithium loss during cycling, paired cells were tested at each charge rate. To determine this, the cells were cycled once at C / 20 before and after the high charge rate segment. minimizes electrolyte oxidation at the negative electrode and prevents the fully loaded negative electrode from accelerating, which occurs in these cells at 4.4V. The upper cutoff voltage was set at 4.1 V to ensure that no leaks were present. To eliminate the effects of small amounts of gas that may be generated during cycling, all pouch cells were externally The clamp cycled the battery. After approximately 350 hours of cycling, or a 20% capacity loss, Once this was reached, the cell was stopped.

[0292] Two-electrolyte system with FEC or VC as additive: In certain embodiments, A two-additive electrolyte system with additive concentrations of approximately 0.25-6% forms part of the battery system. Figure 22 shows the experimental data of plating experiments for different battery systems at different current charging rates. Figure 22 shows that the addition of DTD does not significantly increase the maximum current at which plating can occur. For example, a sample consisting of two additives, i.e., 2% FEC + 1% DTD, The slow capacity loss of the electrolyte system was measured at 1C, 1.5C, and 2C with a single addition. Similarly, Figure 22 shows that the ionic conductivity of the electrolyte system containing the two additives is reduced compared to the electrolyte system containing 2% FEC. The slow capacity loss of the electrolyte system consisting of additives, i.e., 1% FEC + 1% DTD, is 1C and 1.5C, lower than the electrolyte system with a single additive, 2% FEC. This is only slightly higher at 2C.

[0293] Figure 23 shows experimental data from plating tests, showing the charging current every 30 cycles. The mass loss rate indicates lithium plating. At a charging current of 2C, all cells However, the cells with DTDs continued to plate lithium during plating. This is because the amount of plating in the cell with DTD is less than that in the cell without DTD. In addition to DTD, other sulfur-containing compounds also reduce plating can function similarly to reduce

[0294] Figure 24 shows experimental data for peak capacity as a function of cycle number for different electrolyte systems. The results show that DTD is significantly reduced when DTD and MMDS are combined with VC. It performed better than MMDS in maintaining the peak capacity of the drug-electrolyte system.

[0295] Methyl acetate as electrolyte solvent: according to certain embodiments, to reduce plating As a solvent, methyl acetate is used at a concentration of up to 60% by weight. Figure 27 shows the effect of using MA as a solvent in the presence of an electrolyte system consisting of The effect of the presence of MA as a solvent and DTD as an additive on the cell impedance. The results of plating experiments to determine the effect of 0%, 2% 2% additives (VC, FEC, and PES) in electrolyte with 0% and 40% MA The remaining electrolyte of 0% MA is 30% ethylene carbonate and 70% ethyl acetate. The remaining electrolyte is 1.2 M LiPF6 in methyl carbonate. 1.2M LiP in 4% ethylene carbonate and 56% ethyl methyl carbonate The remaining electrolyte of 40% MA is 18% ethylene carbonate and 42% ethylene carbonate. 1.2 M LiPF6 in ethyl methyl carbonate. Figure 28 shows that the low rate capacity loss is small. 27. This is an expanded view of the specific data shown in FIG.

[0296] In Figures 27 and 28, higher capacity loss indicates more lithium plating. Figures 27 and 28 show that even at a 2C charge rate, the presence of MA reduces the slow capacity loss. Therefore, the electrolyte solution containing 20% ​​or 40% MA The system is designed for use in fast charging applications, such as energy storage in vehicles, which may be exposed to high charging current rates. It is a strong candidate for use in applications that require electricity.

[0297] Figures 29, 30, and 31 show experimental data for electrolyte systems containing FEC as an additive. The different datasets are shown in Figure 1. The DTD and / or 29, 30, and 31 show the results of the 1 or 2 additives with FEC. Adding MA to the additive electrolyte system allows for up to 2C to be contained without significant plating. This indicates that higher charging speeds are possible.

[0298] Similarly, Figures 32, 33, and 34 show the results for electrolyte systems containing VC as an additive. The results of the experimental data are shown. The different data sets are based on the DTD and and / or MA. Figures 32, 33, and 34 show the additives with VC or By adding MA to the electrolyte system, the plating temperature can be increased up to 2C without significant plating. This indicates that higher charging speeds will be possible, including

[0299] LFO as an electrolyte additive: Figures 44A-44D include systems containing LFO. The long-term cycling data under fast charging for different electrolyte systems is summarized. As can be seen from the data, the presence of MA reduces the amount of plating. Reduce the possibility of Li plating during fast charging. For example, in Figure 44A, 20%MA+1% An electrolyte system with LFO is more effective than another system with less MA or LFO. The normalized discharge capacity loss is significantly less than that of the plating. Represents.

[0300] [Gas volume measurement] intended use, such as grid storage or energy storage in vehicles, including electric vehicles. Before the cells are used in a given application, a formation process is carried out. During formation, the cells are precisely controlled undergoing repeated charge and discharge cycles, which is necessary to ensure that the electrodes and The purpose of this process is to activate the electrolyte and the catalyst. During the formation, gas is generated. occurs (depending on the specific tolerances allowed by the cell and cell package) It may be necessary to release the gas after the forming process and before use in the application. This usually requires the additional step of breaking the seal and then resealing it. These steps are common to many battery systems, but if possible, gas generation should be minimized. It is desirable to eliminate these by choosing fewer systems.

[0301] Gas volume experiments were recommended to measure gas evolution during formation and cycling. To measure the gas concentration, ex-situ (static) measurements were used. The measurements were performed by immersing the cell in the liquid. The test was carried out using Archimedes' principle by hanging the object from a balance. The change in weight of a cell suspended in a fluid is directly related to the change in volume due to the change in buoyancy force. The change in mass Am of a cell suspended in a fluid of density p is related to the change in cell volume Δν, as expressed by Δν=A Related by m / p.

[0302] Two-electrolyte system with FEC or VC as additive: In certain embodiments, A two-additive electrolyte system with additive concentrations of approximately 0.25-6% forms part of the battery system. Figure 20 shows the results of a gas generation experiment in which the amount of gas generated was measured according to the procedure described above. Figure 20 shows that systems without DTDs usually perform better, e.g. , the system containing only 2% FEC as an additive is 1% FEC + 1% DTD and 2% F EC+1% shows better performance than DTD. That is, DTD is a gas that is forming. Increased volume generation and desirable properties when combined with other additives, e.g., VC and FEC. When DTD is used as an additive for desirable properties, the system is As shown in Fig. 1, a mechanism for safely disposing of gases generated by DTDs, such as gas release after formation, has been developed. Figure 20 shows a two-additive electrolyte system containing MMDS and PES or FEC. stems more (if any) than when 2% PES or FEC was the only additive. This indicates that the catalyst does not produce much additional gas.

[0303] Methyl acetate as electrolyte solvent: according to certain embodiments, to reduce plating As a solvent, methyl acetate is used in concentrations up to 60% by weight. Determine the effect of the presence of MA as a solvent and DTD as an additive on the synthesis gas. The results of gas generation experiments are presented. The electrolyte systems tested were 0%, 20%, and and 2% additives (VC, FEC, and PES) in an electrolyte with 40% MA. The remaining electrolyte of 0% MA was 30% ethylene carbonate and 70% ethyl methyl carbonate. The remaining electrolyte is 20% MA, 1.2M LiPF6 in carbonate, 24% ethylenediaminetetraacetic acid. 1.2M LiPF6 in ethanol carbonate and 56% ethyl methyl carbonate The remaining electrolyte of 40% MA is 18% ethylene carbonate and 42% ethyl methyl methacrylate. 1.2M LiPF6 in carbonate.

[0304] Figure 25 shows the MA in a two-additive electrolyte system containing VC or FEC with DTD. This indicates that the increase in gas volume due to the addition of HCl does not change significantly with increasing amounts of MA. That is, when DTD is part of a two-additive electrolyte system, only VC or FEC Compared to the additive electrolyte system with 1, the critical amount of gas evolved is less. In-Situ Gas Volume Measurement

[0305] Figures 45A and 45B summarize the results of the in-situ gas experiment at 40°C. Cells with LFO but no MA showed less gassing during the hold segment of these tests. This indicates that there is no Cell Impedance

[0306] The two-additive electrolyte system and novel battery system disclosed herein provide low cell The cell impedance reduces the energy efficiency of the cell. It is desirable to minimize the cell impedance. , which means faster charging speeds and higher energy efficiency.

[0307] Cell impedance was measured using electrochemical impedance spectroscopy (EIS). Pouch cells use monocrystalline NMC532 cathodes and synthetic anodes unless otherwise specified. The EIS measurements were performed after the formation of the cell. The cell was then transferred to a temperature box at 10.0±0.1°C. The cells were charged or discharged to 3.80 V before being charged. Signal amplitude: AC input from 100kHz to 10mHz with a resolution of 10 points per decade Impedance spectra were collected. From the measured AC impedance, the charge transfer resistance ( R ct ) was calculated and plotted.

[0308] Two-electrolyte system with FEC or VC as additive: In certain embodiments, A two-additive electrolyte system with additive concentrations of approximately 0.25-6% forms part of the battery system. Figure 21 shows the results from a 1% DTD with 1% or 2% PES, FEC, or VC. Figure 1 shows experimental data from a cell charge transfer impedance experiment of the two-additive electrolyte system. 21 are these 2 of 1% DTD with 1% or 2% PES, FEC, or VC. It was shown that the additive electrolyte system does not significantly increase the cell charge transfer impedance. In particular, 1% DTD with 1% VC, 1% DTD with 2% VC, and 1% FEC The systems with 1% DTD with 2% FEC and 1% DTD with 2% FEC exclude the DTD. The cell impedance was similar to that seen in the single additive system. Therefore, these novel two-additive electrolyte systems exhibit excellent performance. This does not sacrifice the important charge transfer impedance performance.

[0309] Methyl acetate as electrolyte solvent: according to certain embodiments, to reduce plating As a solvent, methyl acetate is used in concentrations up to 60% by weight. The cell culture for the electrolyte system consisting of one-additive and two-additive systems with MA as the additive The results of charge transfer impedance experiments are shown. The additive electrolyte systems tested were 0% DTD and M to electrolyte systems in electrolyte solvents with 20%, 20%, and 40% MA Additives VC, FEC, and PES with and without 1% DTD to show the effect of A The 0% MA electrolyte was 30% ethylene carbonate and 70% ethylene The electrolyte is 1.2 M LiPF in methyl carbonate. The remaining electrolyte is 20% MA. 1.2M Li in 24% ethylene carbonate and 56% ethyl methyl carbonate The remaining electrolyte of 40% MA is 18% ethylene carbonate and 42% 1.2 M LiPF6 in ethyl methyl carbonate. Figure 26 shows that DTD Furthermore, the results show that the DTD produces only a slight increase in dynamic impedance. In the two-additive electrolyte system containing VC or FEC, the addition of MA significantly reduced the cell charge. In 40% MA solvent, VC+DTD and FEC+D The TD system is a charge-dispersion model from the corresponding system without DTD and MA as a solvent. The transfer impedance was decreased. In the PES+DTD2 additive electrolyte system, MA also reduced the charge transfer impedance of the system.

[0310] The above disclosure is not intended to limit the disclosure to the precise forms or particular fields of use disclosed. Therefore, nothing expressly stated or implied herein is intended to Regardless, various alternative embodiments and / or modifications to the present disclosure are contemplated in light of the present disclosure. Having thus described the embodiments of the present disclosure, those skilled in the art will recognize that It will be appreciated that changes may be made in form and detail without departing from the scope of the present disclosure. Therefore, the present disclosure is limited only by the claims. and generally refer to active additives unless otherwise specified in the specification.

[0311] In the foregoing specification, the present disclosure has been described with reference to specific embodiments. As will be appreciated by those skilled in the art, the various embodiments disclosed herein may be implemented in accordance with the spirit and scope of the present disclosure. May be modified or implemented in various other ways without departing from the spirit and scope of Therefore, this description should be considered as illustrative and not as a general guide to the disclosed battery system. It is intended to teach those skilled in the art how to make and use various embodiments. The forms of disclosure shown and described herein should be construed as exemplary embodiments. It is to be understood that equivalent elements or materials may be used in place of those typically shown and described herein. Certain features of the present disclosure may be substituted for those described herein. may be utilized independently of the use of other features, as will become apparent to those skilled in the art after having the benefit of the present invention. "Including" as used to describe and claim this disclosure may be used. "," "comprising," "incorporating" ), "consisting of", "have", "is "(is)" and similar expressions are intended to be inclusive, i.e., There may also be items, components, or elements that are not part of the same word. References to "about" or "approximately" should be construed as including plus or minus. Similarly, any percentage of an additive may be References to tage should be construed to mean plus or minus 10%.

[0312] Moreover, the various embodiments disclosed herein are intended to be illustrative and explanatory. and should not be construed as limiting the disclosure in any way. References (e.g., attached, fastened, coupled, connected, etc.) will aid the reader in understanding this disclosure. and is used solely for the purpose of, and in particular for, the location, arrangement, and performance of, the systems and / or methods disclosed herein. Therefore, references to combinations are not intended to create limitations on the direction or use of the In addition, any reference to such a combination shall be interpreted broadly. It is not intended to imply that the elements are directly connected to each other.

[0313] Additionally, terms such as "first," "second," "tertiary," "primary," "secondary," "main," or similar may be used. any other ordinary and / or numerical terms, such as, but not limited to All numerical terms also refer to the various elements, embodiments, variations, and / or To aid the reader's understanding of the amendment, it should be interpreted only as an identifier and not as a separate element. Any elements, embodiments, variations, and / or modifications to the and / or amendments, particularly as to the order or priority of stomach.

[0314] Also, one or more of the elements shown in the drawings / figures may be modified to suit a particular application. It may be implemented in a more divided or integrated manner, or may be omitted or moved in certain cases. It is also possible to remove it as inoperable. [Prior art documents] [Patent documents]

[0315] [Patent Document 1] US Patent Application Publication No. 2017 / 0025706 [Non-patent literature]

[0316] [Non-Patent Document 1] JC Burns et al., Journal of the Electrochemical Society, 160, A1451 (2013)

Claims

1. a lithium salt, a first non-aqueous solvent, a first active additive of lithium difluorophosphate, and and a second active ingredient of either fluoroethylene carbonate or vinylene carbonate. and an additive mixture comprising an additive.

2. 2. The non-aqueous composition of claim 1, wherein the concentration of the first effective additive is in the range of 0.25 to % by weight. Aqueous electrolyte.

3. 3. The method of claim 2, wherein the concentration of the second effective additive is in the range of 0.25 to 6% by weight. Non-aqueous electrolytes.

4. 4. The non-aqueous electrolyte of claim 3, wherein the non-aqueous electrolyte does not include a third active additive.

5. The non-aqueous electrolyte of claim 4 , wherein the first non-aqueous solvent is a carbonate solvent.

6. 6. The non-aqueous electrolyte of claim 5, further comprising a second non-aqueous solvent of methyl acetate.

7. 7. The non-aqueous electrolyte of claim 6, wherein the second active additive is vinylene carbonate. 。

8. 4. The non-aqueous electrolyte of claim 3 further comprising a second non-aqueous solvent of methyl acetate.

9. a negative electrode; A positive electrode and a non-aqueous electrolyte comprising lithium ions dissolved in a first non-aqueous solvent and an additive mixture; and, The additive mixture comprises: a first active additive of lithium difluorophosphate; A second active ingredient of either fluoroethylene carbonate or vinylene carbonate. A lithium ion battery comprising: an additive;

10. 0.25% by weight or more of tris(trimethylsilyl) phosphate and tris(trimethylsilyl) phosphite 10. The lithium ion battery of claim 9, excluding active additives of methylsilyl.

11. 10. The method of claim 9, wherein the concentration of the first effective additive is in the range of 0.25 to 6 wt. %. Lithium-ion battery.

12. 12. The method of claim 11, wherein the concentration of the second effective additive is in the range of 0.25 to 6 wt. %. Lithium-ion battery.

13. 13. The lithium-ion electrolyte of claim 12, wherein the non-aqueous electrolyte does not include a third active additive. battery.

14. 14. The lithium-ion battery of claim 13, wherein the first non-aqueous solvent is a carbonate solvent. battery.

15. 15. The lithium-ion battery of claim 14, further comprising a second non-aqueous solvent of methyl acetate. pond.

16. The positive electrode is made of NMC532 or NM 16. The lithium ion battery of claim 15, comprising either C622 or C622.

17. 17. The cathode of claim 16, wherein the cathode is coated with aluminum oxide or titanium dioxide. Lithium-ion battery included.

18. 18. The lithium-ion battery of claim 17, further comprising a second non-aqueous solvent of methyl acetate. pond.

19. a negative electrode; a positive electrode comprising an NMC having micrometer-scale particles; a non-aqueous electrolyte comprising lithium ions dissolved in a first non-aqueous solvent and an additive mixture; and, The additive mixture comprises: The first effective one of either fluoroethylene carbonate or vinylene carbonate Additives and 1,3,2-dioxathiolane-2,2-dioxide, another sulfur-containing additive, or and a second active additive of either lithium difluorophosphate. pond.

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