Electrochemically in situ formed rocksalt phase in titanium dioxide determines pseudocapacitive sodium-ion storage
Dafu Tang, Ruohan Yu, Yalong Jiang, Jiantao Li, Zerui Yan, Sicheng Fan, Xiaojuan Huang, Sungsik Lee, Tianyi Li, Qingshui Xie, Liqiang Mai, Dong‐Liang Peng, Qiulong Wei
Abstract
Earth-abundant TiO2 is a promising negative electrode for low-cost sodium-ion batteries (SIBs) owing to its high capacity, rapid (dis)charging capability, safe operation potential and nonflammability. Crystalline anatase TiO2 is not suitable for reversible Na+ (de)intercalation, but it displays pseudocapacitive response after repeated cycles. Herein, we find and demonstrate that ordered rocksalt (RS) NaTiO2 nanograins are in situ formed by electrochemically cycling with Na+ ions in anatase and amorphous TiO2. The in situ formed RS-NaTiO2 follows a solid-solution reaction with small volume changes of only 2.0%, that determines the pseudocapacitive “mirror-like” cyclic voltammetry curve with a couple of broad redox peaks at 0.75 V vs. Na+/Na, a high capacity of 253 mAh g−1, high-rate capability and thousands of stable cycles. The multistep crystalline-to-amorphous-to-RS transformations are able to be electrochemically activated during the aging process of assembled full cells. Our finding provides a direction for developing unconventional Ti-based high-performance active materials for SIBs with both high energy and power densities. Earth-abundant TiO2 is a promising negative electrode material for low-cost sodium-ion batteries. Here, authors show that ordered rocksalt NaTiO2 nanograins are in situ formed by electrochemically cycling with Na+ ions in anatase TiO2, which determines the pseudocapacitive high-rate capability.