Dialing in the Voltage Window: Reconciling Interfacial Degradation and Cycling Performance Decay with Cation-Disordered Rocksalt Cathodes

Lithium-excess, cation-disordered rocksalt (DRX) materials have received considerable interest as cathode materials for Li-ion batteries, owing to their high specific capacity and compositional flexibility. Despite these advantages, high interfacial reactivity of DRX materials causes extensive oxidative electrolyte degradation at the cathode-electrolyte interface. In addition to consuming electrolyte, this interfacial degradation is likely to lead to a cascade of deleterious effects throughout the cell, as reactive degradation products drive secondary degradation processes like dissolution of transition metals and decomposition of passivating interfacial species. While in-situ gas evolution measurements conducted by differential electrochemical mass spectrometry (DEMS) allow for the observation and quantification of the degradation processes occurring at the DRX surface, the customized cell configuration with which the technique is conducted is not well suited for capturing the performance decay driven by the interfacial degradation. In particular, a large excess of electrolyte and a large Li metal counter-electrode, both of which are necessary features of DEMS cells, serve to mask the deleterious effects of the interfacial degradation on electrochemical performance. In this work, we reconcile the degradation observed by DEMS with performance decay measured by extended cycling experiments in electrolyte-lean full cells. By comparing DRX outgassing and cycling performance in different voltage windows, we demonstrate a positive correlation between the extent of outgassing and the rate of DRX performance decay during cycling. This result provides a crucial link between the degradation measured by techniques like DEMS and the performance decay measured by cycling experiments, and it allows for the fine-tuning of a cycling voltage window which optimizes the tradeoff between initial performance and long-term stability. Furthermore, this work emphasizes the importance of cell design features, like electrolyte volume and counter-electrode material, and their impact on different electrochemical experiments.