Deciphering the Lithium‐Ion Conduction Mechanism of LiH in Solid‐Electrolyte Interphase

Abstract Lithium hydride (LiH) has been widely recognized as the critical component of the solid‐electrolyte interphase (SEI) in Li batteries. Although the formation mechanism and structural model of LiH in SEI have been extensively reported, the role in electro‐performance of LiH in SEI is still ambiguous and has proven challenging to explored due to the complicated structure SEI and the lack of advanced in situ experimental technology. In this study, the isotopic exchange experiments combined with isotopic tracer experiments is applied to solidly illustrate the superior conductivity and Li + conduction behavior of the LiH in natural SEI. Importantly, in situ transmission electron microscopy analysis is utilized to visualize the self‐electrochemical decomposition of LiH, which is significantly distinctive from LiF and Li 2 O. The critical experimental evidence discovered by the work demonstrates ion transport behaviors of key components in the SEI, which is imperative for designing novel SEI and augurs a new area in optimizing the performance of lithium batteries.