LAUSR

The cycling stability of batteries is closely related to the dynamic evolution of solid electrolyte interphases (SEIs) in response to the discharging/charging processes. Here, the state‐of‐the‐art cryogenic transmission electron microscopy (cryo‐TEM) and spectroscopy are utilized to probe the SEI breathing behavior induced by discharging/charging on the conversion‐type anode made of Fe2O3 quasi‐cubes. The incorporation of the identical‐location strategy allows the tracking of the evolution of the same SEIs at different charge states. SEI breathing is shown to involve swelling (contracting) upon lithiation (de‐lithiation) driven by the reversible compositional change. Bare Fe2O3 anodes develop an unstable SEI layer due to the intermixing with the lithiation product Li2O, which exhibits a large thickness variation upon breathing as well as excessive growth. A transition from organic to inorganic‐type SEI is also identified upon cycling, which gives rise to significantly increased SEI resistance. To tailor the SEI behavior, N‐doped carbon coating is applied on Fe2O3 (Fe2O3@CN), which can effectively separate the lithiation product from SEI. A thinner and chemically more stable SEI layer develops on Fe2O3@CN, resulting in remarkably enhanced cycling stability compared to bare Fe2O3. This work demonstrates the importance of understanding and optimizing the dynamic behavior of SEIs to achieve better battery performance.