Understanding Li Plating and Stripping Behavior in Zero-Excess Li Metal Batteries Using Operando Dilatometry

Zero-excess Li metal batteries (ZELMB), in which the Li-metal anode is plated in situ on the anode current collector during initial charging, have received considerable attention in recent years. Such batteries hold enormous potential for increasing energy density and simplifying battery production, thus reducing costs, material, and energy requirements. However, transfer into application has so far been limited by challenges related to the non-uniform deposition behavior of lithium, which leads to inadequate performance and safety concerns. To meet these challenges, the electrochemical deposition behavior of lithium must be very well understood to derive and evaluate knowledge-based optimization approaches. For this purpose, advanced characterization methods are urgently needed. Herein the use of operando electrochemical dilatometry (OED) to study Li deposition and dissolution in ZELMB is demonstrated. We show how OED not only provides information on thickness changes during Li deposition and stripping, but also allows insights regarding morphology evolution and quantification of dead Li. The present work is intended to serve as an example to demonstrate the valuable insights that can be gained with OED and to encourage the scientific community to use it to support the development of advanced Li-, Na-, or K-metal batteries.