Tailoring Redox Reactions for Stable Cycling of High-Capacity Li-Ion Cathodes

Abstract

Development of new cathode materials with even better performance and lower cost is needed to meet the ever-increasing global demand on lithium-ion batteries. As such, extensive efforts have been devoted to developing next-generation cathodes for high-energy Li-ion batteries, e.g., Li-rich transition metal oxides. As a counterpart to the conventional cation-ordered layered oxides, cation-disordered rocksalts (DRXs) have emerged as a new class of high-capacity cathode materials. One unique advantage of the DRX chemistry is the structural flexibility that substantially lessens the elemental constraints and enables the incorporation of a wide variety of TMs and fluorine anion at a decent amount in the crystal lattice. As a result, the dominant TMs have been extended from redox-active Ni and Co in layered cathodes to cost-effective and earth-abundant Mn and Fe as well as redox-inactive TM (e.g., Nb, Ti, Zr, Mo) to facilitate the DRX phase formation. This exceptional chemical diversity largely opens up the opportunity to tune the material compositions for optimal performance through the control of redox reactions.In this talk, I will present our recent work on several high-capacity cathodes based on Mn and Ni redox centers. We specifically focused on understanding the redox chemistry, including cationic and anionic redox, using combined electrochemical, soft X-ray absorption (XAS), and resonant inelastic X-ray spectroscopy (RIXS) techniques. This presentation summarizes the different TM and O redox behaviors and their roles in the electrochemical processes of these high-capacity cathodes. I will then show some examples on how this understanding leads to improved cathodes with enhanced performance by tailoring the redox reactions.