Dual-Site Doping in Transition Metal Oxide Cathode Enables High-Voltage Stability of Na-Ion Batteries.

Designing cathode materials that effectively enhancing structural stability under high voltage is paramount for rationally enhancing energy density and safety of Na-ion batteries. This study introduces a novel P2-Na 0.73 K 0.03 Ni 0.23 Li 0.1 Mn 0.67 O 2 (KLi-NaNMO) cathode through dual-site synergistic doping of K and Li in Na and transition metal (TM) layers. Combining theoretical and experimental studies, this study discovers that Li doping significantly strengthens the orbital overlap of Ni (3d) and O (2p) near the Fermi level, thereby regulates the phase transition and charge compensation processes with synchronized Ni and O redox. The introduction of K further adjusts the ratio of Na e and Na f sites at Na layer with enhanced structural stability and extended lattice space distance, enabling the suppression of TM dissolution, achieving a single-phase transition reaction even at a high voltage of 4.4 V, and improving reaction kinetics. Consequently, KLi-NaNMO exhibits a high capacity (105 and 120 mAh g -1 in the voltage of 2-4.2 V and 2-4.4 V at 0.1 C, respectively) and outstanding cycling performance over 300 cycles under 4.2 and 4.4 V. This work provides a dual-site doping strategy to employ synchronized TM and O redox with improved capacity and high structural stability via electronic and crystal structure modulation.