First-Principles Modeling of Sodium Ion and Water Intercalation into Titanium Disulfide Interlayers for Water Desalination

Recent experiments revealed the possibility of using titanium disulfide (TiS2) as the cathode material in capacitive deionization (CDI) devices for water desalination. Although it performed stably up to 70 cycles with a salt removal capacity of 14 mg/g (corresponding to a sodium ion removal capacity of 35.8 mg/g) at high molar concentration (600 mM NaCl), the maximum capacity of TiS2 as a CDI electrode was much lower (∼70 mAh/g) than as a supercapacitor (239 mAh/g). Understanding why the ion capacities of these two configurations of the same material differ will entail elucidating detailed charge/discharge mechanisms at the atomic scale. Here, we present density functional theory simulations of sodium intercalation into TiS2 interlayers in order to gain such understanding. We systematically investigated TiS2 stacking patterns and ion intercalation sites, energetics of the intercalated compounds, and phase transformation during sodium intercalation. The calculated structural evolution and capacitance-voltage curve agree quite well with previous measurements. We conclude that the different maximum capacities of TiS2 measured in aqueous and dry environments originate from weaker interlayer interactions with respect to shear strain after ∼33% intercalation of Na+-H2O pairs, which is detrimental to the mechanical stability of TiS2. This study sheds light on the underlying mechanisms of ion intercalation into layered materials and contributes to understanding requirements for future design and optimization of CDI electrode materials for water desalination.