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Flammability studies of electrolytes are required for screening safer materials used in lithium-ion batteries. Besides the thermal stability, the effects of lithium salts on electrolyte combustion are important as well for fire safety of electrolytes. To clarify the influence of lithium salts on the electrolyte flammability, experimental analyses were conducted using a unique wick combustion system in conjunction with the limiting oxygen concentration (LOC) test, called wick-LOC method. The dimethyl carbonate (DMC)-based electrolytes with 1M addition of different lithium salts (LiPF6, LiBF4, and LiTFSI) were studied comparing with pure DMC and trimethyl phosphate (TMP)-added solvents. The three lithium salts gave unique and distinct flame behaviors including flame shapes, colors and the changes of wick surface until self-extinguishing. The wick-LOC results indicated a considerable flame-retardant effect of LiPF6, while other salts have minor effects on the flame extinction. Utilizing the flame spectrum and combustion residue analyses, the roles of salts during combustion were characterized. The PF6 anion played a similar role with the TMP additive in the gas phase flame inhibition. In the cases of LiPF6 and LiBF4, the solid products (LiF) accumulation blocked the fuel supply from the wick to the flame region. In the case of LiTFSI, the serious charring of the cotton wick was considered as a potential hazard on solid combustibles in the real fire scenarios.

To quantify the flammability limits of organic electrolyte solvents used in lithium-ion batteries, a unique wick combustion system was developed in conjunction with limiting oxygen concentration (LOC) of candle-like flame, named wick-LOC method. By controlling the oxygen-nitrogen ratio of external flow of the wick diffusion flame, the flammability limits (LOC) of electrolyte solvents were determined experimentally. To provide reproducible results under specified conditions, the effects of axial flow velocity, exposed wick length and elapsed time after ignition on the wick-LOC were studied, and the proper experimental conditions were selected for further applications. To validate the reliability of wick-LOC in flammability evaluation, correlation analyses to other flammability properties (flash point, auto-ignition temperature, the heat of combustion and other types of LOC) were conducted. The wick-LOC method was then applied to quantify the flammability of mixed solvents. The linear changes of wick-LOC with mixing ratios were found in the mixture of linear and cyclic carbonates, while the non-linear trends were found in carbonate-ether mixed solvents. To evaluate the flame-retardant effectiveness of organophosphorus compounds (OPCs) as additives in electrolyte solvents, a series of tests were conducted. Results showed that small amounts of OPCs had significant flame-retardant effects, but the efficiency decreased with the higher OPC additions. The effectiveness of four OPCs was distinguished as well. The results of this work provided valuable information about the flammability limits of single and mixed electrolyte solvents, and it may be useful for designing electrolyte balanced in both performance and safety.

An investigation was conducted to study wick combustion of Li and SF6. A single-line laser induced fluorescence thermometry with Li2 as fluorescence species was developed. Wick combustion of Li and SF6 was conducted in vacuum chamber at sub-atmospheric pressures. The combustion results in a bright pinkish flame. Emission spectra shoe that the flame luminosity is dominated by the resonance-emission line of Li atoms. On analysis, a conserved scalar approach was employed to model the wick flame. A single equation was obtained to describe the interface condition of wick combustion. Numerical solutions were obtained for laminar wick diffusion flames. The prediction yields similarity profiles for planar Li-SF6 wick diffusion flames, but similarity solutions are not obtained for cylindrical wick diffusion flames. Cylindrical wick diffusion flames are found to deviate substantially from the planar geometry. The effects on mass burning rates due to fuel composition variations were studied employing fuel-rich and product-rich liquids at 0.0035 MPa in the analysis. Product-rich fuel yielded a much lower flame temperature; the mass burning rate, however, was higher than the pure lithium at 0.01 MPa. Results suggest that wick configuration may achieve a higher fuel utilization than the submerged jet.