Thermodynamics Research Center / ThermoML | Journal of Chemical Thermodynamics

ABSTRACT

The methane solubility in five pure electrolyte solvents and one binary solvent mixture for lithium ion batteries such as ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC) and the (50:50 wt%) mixture of EC:DMC was studied experimentally at pressures close to atmospheric and as a function of temperature between (280 and 343) K by using an isochoric saturation technique. The effect of the selected anions of a lithium salt LiX (X = hexafluorophosphate, PF 6 ; tris(pentafluoroethane)trifluorurophosphate, FAP ; bis(trifluoromethylsulfonyl) imide, TFSI ) on the methane solubility in electrolytes for lithium ion batteries was then investigated using a model electrolyte based on the binary mixture of EC:DMC (50:50 wt%) + 1 mol dm 3 of lithium salt in the same temperature and pressure ranges. Based on experimental solubility data, the Henry s law constant of the methane in these solutions were then deduced and compared together and with those predicted by using COSMO-RS methodology within COSMOthermX software. From this study, it appears that the methane solubility in each pure solvent decreases with the temperature and increases in the following order: EC less than PC less than EC:EMC (50:50 wt%) less than DMC less than EMC less than DEC, showing that this increases with the van der Walls force in solution. Additionally, in all investigated EC:DMC (50:50 wt%) + 1 mol dm 3 of lithium salt electrolytes, the methane solubility decreases also with the temperature and the methane solubility is higher in the electrolyte containing the LiFAP salt, followed by that based on the LiTFSI one. From the variation of the Henry s law constants with the temperature, the partial molar thermodynamic functions of solvation, such as the standard Gibbs free energy, the enthalpy, and the entropy where then calculated, as well as the mixing enthalpy of the solvent with methane in its hypothetical liquid state. Finally, the effect of the gas structure on their solubility in selected solutions was discussed by comparing methane solubility data reported in the present work with carbon dioxide solubility data available in the same solvents or mixtures to discern the more harmful gas generated during the degradation of the electrolyte, which limits the battery lifetime.