Qingshan Xie, Xinyu Hou, Wendi Dong, Langyuan Wu, Z. X. Li, Yuhao Zhou, Wenjian Zhang, Shuangyi zhang, Xiaogang Zhang
O3-type layered oxides are promising cathodes for sodium-ion batteries (SIBs), but their practical deployment is hindered by structural degradation and voltage decay during cycling. Here, we investigate a high-entropy, O3-type layered oxide series with systematically varied Ti contents to examine how a nominally electrochemically inactive cation influences framework stability and electrochemical reversibility. The optimized composition, NaNi 0.4 Mn 0.3 Fe 0.1 Ti 0.1 Li 0.05 Sb 0.05 O 2 (HEO-Ti10), delivers long-cycle stability (∼80% capacity retention after 200 cycles at 150 mA g −1 ) and high rate capability (113 mAh g −1 at 1.5 A g −1 ). Structural and spectroscopic analyses─including in situ/ex-situ XRD, XAFS, and TEM─indicate that moderate Ti incorporation enhances lattice robustness, suppresses irreversible phase evolution, and mitigates instability associated with Mn-site octahedral distortion signatures. These findings highlight a compositional tuning strategy within high-entropy layered oxides and may inform the rational design of stable and high-performance cathodes for practical SIBs applications.