LAUSR

Two-dimensional (2D) metal sulfides show great promises for their potential applications as electrode materials of sodium ion batteries because of the weak interlayer van der Waals interactions which allow the reversible accommodation and extraction of sodium ions. The sodiation of metal sulfides can undergo a distinct process compared to that of lithiation, which is determined by their metal and structural types. However, the structural and morphological evolution during its electrochemical sodiation is still unclear. Here, we studied the sodiation reaction dynamics of TiS2 by employing in situ transmission electron microscopy and first-principles calculations. During the sodium ion intercalation process, we observed multiple intermediate phases (phase II, phase Ib, and phase Ia), different from its lithiation counterpart, with varied sodium occupation sites and interlayer stacking sequences. Further insertion of Na ions prompted a multi-step extrusion reaction which led to the phase separation of Ti metal from the Na2S matrix, with its 2D morphology expanded to a 3D morphology. In contrast to regular conversion electrodes, TiS2 still maintained a compacted structure after a full sodiation. Frist-principles calculations reveal that the as-identified phases are thermodynamically preferred at corresponding intercalation/extrusion stages compared to other possible phases. The present work provides the fundamental mechanistic understanding of the sodiation process of 2D transition metal sulfides.