Multistep Lithiation of Tin Sulfide: An Investigation Using in Situ Electron Microscopy.

Two-dimensional (2D) metal sulfides have been widely explored as promising electrodes for lithium-ion batteries since their two-dimensional layered structure allows lithium ions to intercalate between layers. For tin disulfide, the lithiation process proceeds via a sequence of three different types of reactions: intercalation, conversion, and alloying, but the full scenario of reaction dynamics remains nebulous. Here, we investigate the dynamical process of the multistep reactions using in situ electron microscopy and discover the formation of an intermediate rock-salt phase with the disordering of Li and Sn cations after initial 2D intercalation. The disordered cations occupy all the octahedral sites and block the channels for intercalation, which alter the reaction pathways during further lithiation. Our first-principles calculations of the nonequilibrium lithiation of SnS corroborate the energetic preference of the disordered rock-salt structure over known layered polymorphs. The in situ observations and calculations suggest a two-phase reaction nature for intercalation, disordering, and following conversion reactions. In addition, in situ delithiation observation confirms that the alloying reaction is reversible, while the conversion reaction is not, which is consistent with the ex situ analysis. This work reveals the full lithiation characteristic of SnS and sheds light on the understanding of complex multistep reactions in 2D materials.