Enhancing the Structural Stability and Diffusion Kinetics of a Tunnel-Phase Cathode by the Synergistic Effect of Cation-Anion Co-Doping for Advanced Sodium-Ion Batteries

Tunnel-structured Na_0.44MnO₂ (NMO) has been extensively studied as a potential cathode for sodium-ion batteries (SIBs) due to its favorable cycling endurance, cost-effectiveness, environmental benignity, and notable air-moisture stability. However, limitations, such as sluggish ion diffusion kinetics, an insufficient Na⁺ storage capacity, and an unsatisfactory Jahn-Teller effect, impede its widespread application. To address these problems, this study proposes a co-doping strategy that involves the simultaneous introduction of a cation and an anion. The optimized cathode Na_0.44Mn_0.99Ni_0.01O_1.985F_0.015 demonstrates remarkable rate capabilities with average discharge capacities of 136.2, 133.0, 129.6, 124.0, 115.9, and 95.8 mAh g^-1 under current rates ranging from 0.1 to 5 C. Furthermore, it also exhibits exceptional long-term cyclability, retaining 86.5% and 89.4% capacity retention at 1 and 5 C after 200 and 400 cycles, respectively, accompanied by nearly 100% Coulombic efficiency. A comprehensive structural characterization and experimental analysis reveal that the synergistic incorporation of Ni and F can effectively adjust the lattice parameters and alleviate the Jahn-Teller distortion of the NMO cathode, thereby resulting in enhanced structural integrity, rapid ion transfer dynamics, and excellent sodium storage performance. Consequently, this investigation establishes a significant approach for optimizing tunnel-phase Mn-based cathodes through the synergistic effect of cation and anion co-doping, which promotes the practical implementation of advanced SIBs.