Haofei Yang, Wenbin Li, Jintao Xu, Yetong Li, Mengjiao Li, Jianhua Zhang, Yangyang Luo, Qinting Jiang, Lingkun Yang, Jiaxuan Zuo, Xuexia Song, Jingjing Wang, Xifei Li
Layered sodium vanadate has attracted considerable attention as a promising cathode material for sodium-ion batteries, due to its multiple accessible vanadium valence states and large interlayer spacing. However, its inherent limitations in electronic/ionic conductivity and lattice stability result in poor Na + storage stability. To address these challenges, a coupled electronic and lattice modulation strategy is proposed, in which metal-ion pre-intercalation is employed to tune the electronic structure of lattice oxygen. It is revealed that Zn 2+ pre-intercalation elevates the p-band center of lattice O (Oεp) by forming the interlayer local coordination structure of ZnO 4 tetrahedral. This electronic modulation simultaneously increases both oxygen vacancy formation energy and Na + adsorption energy, leading to two critical improvements of significant suppression of potential attenuation and enhanced Na + transport kinetics. Furthermore, the Oεp position serves as a critical descriptor for Na + storage stability, exhibiting an approximately linear correlation with both average potential retention and capacity retention. Consequently, Zn 2+ pre-intercalated cathode exhibits outstanding long-term cycling stability, achieving a high capacity retention of 81.2% after 500 cycles at 1.65 A g −1 , with potential attenuation nearly eliminated. This study advances both the fundamental understanding and practical design of layered oxide cathodes through structural modification for enhanced cycling stability. • The newly developed layered sodium vanadate cathode demonstrates an outstanding capacity retention of 81.2% after 500 cycles at a high current density of 1.65 A g −1 . • Zn 2+ pre-intercalation effectively elevates the O p-band center (Oεp) by forming the interlayer local coordination structure of ZnO 4 tetrahedral. • The p-band center of lattice O (Oεp) is found to be a key descriptor for Na + storage stability, exhibiting approximate linear correlation with both average potential retention and capacity retention.