Crystal Modulation of Mn-Based Layered Oxide toward Long-Enduring Anionic Redox with Fast Kinetics for Sodium-Ion Batteries.

Abstract

Mn-based layered oxide cathodes for sodium-ion batteries with anionic redox reactions hold great potential for energy storage applications due to their ultra-high capacity and cost effectiveness. However, achieving high capacity requires overcoming challenges such as oxygen-redox failure, sluggish kinetics, and structural degradation. Herein, we employ an innovative crystal modulation strategy, using Mn-based Na0.72Li0.24Mn0.76O2 as a representative cathode material, which shows that the highly exposed {010} active facets enable an enhanced rate capability (119.6 mAh g-1 at 10C) with fast kinetics. Meanwhile, the reinforced Mn-O bond inhibits excessive oxidation of lattice oxygen and O-O cohesion loss, stabilizing and maintaining a long-enduring reversible oxygen-redox activity (100% high capacity retention after 100 cycles at 0.5C and 84.28% retention after 300 cycles at 5C). Time-resolved operando two-dimensional X-ray diffraction reveals the robust structural stability, zero-strain behavior, and suppressed phase transition with ultra-low volume variation during cycling at different rates (0.1C: 1.75%, 1C: 0.31%, 5C: 0.04%). Additionally, the full cell coupled with hard carbon achieves a high energy density of approximately 211 Wh kg-1 with superior performance. This work highlights the significance of crystal modulation and presents a universal approach in developing Mn-based oxide cathodes with stable anionic redox for high-performance sodium-ion batteries.