In Situ Characterization of Over-Lithiation of Organosulfide-Based Lithium Metal Anodes

Over-lithiated organosulfides, such as sulfurized polyacrylonitrile (SPAN), are promising candidates of lithium metal anode (LMA) protection since they could form robust solid electrolyte interphases (SEIs), which is the key toward stable lithium metal batteries. So far, the mechanism of over-lithiation and evolution of the electrode surface is poorly understood. Herein, several in situ techniques were employed to study the over-lithiation process in SPAN, including in situ Raman spectroscopy to reveal the chemical transformation and in situ electrochemical atomic force microscopy (EC-AFM) to visualize interfacial evolution. The results undoubtedly prove the breaking of the C–S bond and formation of the C–Li bond during the over-lithiation process. The nucleophilic C–Li could further trigger the decomposition of the electrolyte to form an inorganic–organic hybrid SEI on the surface of SPAN, which allows uniform Li deposition and significantly improves the cycle stability of LMAs, as supported by the in situ EC-AFM characterization as well as a series of full cell tests. New insights into the over-lithiation mechanism of SPAN should facilitate the design of organosulfides to construct stable lithium metal anodes.