Boosting the Reversibility and Kinetics of Anionic Redox Chemistry in Sodium-Ion Oxide Cathodes via Reductive Coupling Mechanism

Activating anionic redox chemistry in layered oxide cathodes is a paradigmatic approach to devise high-energy sodium-ion batteries. Unfortunately, excessive oxygen redox usually induces irreversible lattice oxygen loss and cation migration, resulting in rapid capacity and voltage fading and sluggish reaction kinetics. Herein, the reductive coupling mechanism (RCM) of uncommon electron transfer from oxygen to copper ions is unraveled in a novel P2-Na0.8Cu0.22Li0.08Mn0.67O2 cathode for boosting the reversibility and kinetics of anionic redox reactions. The resultant strong covalent Cu–(O–O) bonding can efficaciously suppress excessive oxygen oxidation and irreversible cation migration. Consequently, the P2-Na0.8Cu0.22Li0.08Mn0.67O2 cathode delivers a marvelous rate capability (134.1 and 63.2 mAh g–1 at 0.1C and 100C, respectively) and outstanding long-term cycling stability (82% capacity retention after 500 cycles at 10C). The intrinsic functioning mechanisms of RCM are fully understood through systematic in situ/ex situ characterizations and theoretical computations. This study opens a new avenue toward enhancing the stability and dynamics of oxygen redox chemistry.