Formation of LiF Surface Layer During Direct Fluorination of High-Capacity Co-Free Disordered Rocksalt Cathodes.

Abstract

Disordered rocksalt (DRX) cathodes have attracted interest due to their high capacity and compositional flexibility (e.g., Co-free chemistries). However, the sloping voltage profile and gradual capacity fade during cycling have hindered the widespread adoption of these materials. Simulations predict that fluorine substitution in DRX cathodes will improve their capacity, rate performance, and cyclability. In this study, we use a fluidized bed reactor to fluorinate a model Li-rich DRX composition (Li1.15Ni0.375Ti0.375Mo0.1O2, NTMO) to investigate how fluorine content impacts the cathode's structure and electrochemical performance. Instead of substituting O with F to form oxyfluoride phases, direct fluorination of DRX cathodes leads to the formation of LiF surface films, which improves the specific energy and capacity retention. This study demonstrates the feasibility of direct fluorination to improve the electrochemical performance of high-voltage cathodes by tuning the material's surface chemistry.