Interfacial Deterioration in Highly Fluorinated Cation-Disordered Rock-Salt Cathode: Carbonate-Based Electrolyte vs. Ether-Based Electrolyte

Abstract

Cation-disordered rock-salts (DRX) emerge as an intriguing class of high-capacity cathode materials, garnering significant attention in the development of advanced energy-storage systems. Fluorination strategies have been raised to regulate redox and structure for better DRX electrochemical performance. However, research on the interfacial processes during fluorinated DRX cycling remains limited. Here, we evaluate a highly fluorinated DRX, Li2Mn2/3Nb1/3O2F (LMNOF), in different electrolytes to correlate its cycling performance with distinct interfacial evolutions. During cycling in the carbonate-based electrolyte, a thick Mn-containing CEI forms on the LMNOF surface, leading to gradual capacity decay. Intriguingly, the addition of fluoroethylene carbonate (FEC) would bring about surface oxygen loss, Mn-ion dissolution and formation of a fluorinated surface layer by reacting with the LMNOF surface, which critically deteriorate the cycling performance. In comparison, the ether-based electrolyte is compatible with the LMNOF surface, resulting in a more favorable cycling stability. This work sheds light on the interfacial deterioration mechanism of LMNOF cathode in traditional carbonate-based electrolyte, emphasizing the importance of using advanced non-reactive electrolytes to enhance DRX performance.