Adv. Mater.: Enabling High Reversibility of Both Cationic and Anionic Redox in Layered Oxide Cathodes via NiMn6 Superlattice Topology for Sodium-Ion Batteries

Authors：

Zhonghan Wu¹, Youxuan Ni¹, Na Jiang¹, Jinhan Li¹, Limin Zhou², Lunhua He³, Liang Zhang⁴*, Kai Zhang¹*, Fangyi Cheng¹*, and Jun Chen¹

Institutions：

¹State Key Laboratory of Advanced Chemical Power Sources, Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Renewable Energy Conversion and Storage Center (RECAST), College of Chemistry, Nankai University, Tianjin 300071, China.

²School of Energy and Power Engineering, Nanjing University of Science and Technology, Nanjing 210094, China.

³Beijing National Laboratory for Condensed Matter Physics Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China.

⁴Institute of Functional Nano&Soft Materials (FUNSOM), Soochow University, Suzhou 215123, China.

Abstract：

High-voltage oxygen anionic redox provides a transformative opportunity to achieve high energy density of batteries. However, it is challenging to guarantee the reversibility of both cationic and anionic redox for layered transition metal (TM) oxide cathode materials due to the high oxygen-redox reactivity and the complex structural rearrangements. Herein, a honeycomb-layered Na_0.78Ni_0.12Li_0.18Mn_0.7O₂(NNLMO) cathode material with the NiMn₆and LiMn₆dual-topology superlattice is proposed for sodium-ion batteries. The theoretical and experimental studies demonstrate that the Ni²⁺electronic configuration serves as a redox buffer to tune the cationic and anionic redox activity by enlarging the energy gap between O 2pand Mn 3dorbitals, while the NiMn₆topology renders the LiMn₆topology delocalized in the TM layers to reinforce the superstructure stability through suppressing the intralayer Mn migration and O₂formation. As a result, NNLMO delivers a highly reversible capacity of 224 mAh g⁻¹with the mitigated voltage hysteresis and exhibits remarkable capacity retention of 92.2% over 50 cycles within the wide voltage range of 1.5–4.5 V. The findings suggest a new insight into the topological superstructure design of high-energy oxide cathode materials for sustainable batteries.

IF：

27.4

Link：

https://advanced.onlinelibrary.wiley.com/doi/full/10.1002/adma.202419137