A Rational Biphasic Tailoring Strategy Enabling High‐Performance Layered Cathodes for Sodium‐Ion Batteries

Layered oxide cathodes usually exhibit high compositional diversity, thus providing controllable electrochemical performance for Na-ion batteries. These abundant components lead to complicated structural chemistry, closely affecting the stacking preference, phase transition and Na+ kinetics. With this perspective, we explore the thermodynamically stable phase diagram of various P2/O3 composites based on a rational biphasic tailoring strategy. Then a specific P2/O3 composite is investigated and compared with its monophasic counterparts. A highly reversible structural evolution of P2/O3-P2/O3/P3-P2/P3-P2/Z/O3'-Z/O3' based on the Ni2+ /Ni3.5+ , Fe3+ /Fe4+ and Mn3.8+ /Mn4+ redox couples upon sequential Na extraction/insertion is revealed. The reduced structural strain at the phase boundary alleviates the phase transition and decreases the lattice mismatch during cycling, endowing the biphasic electrode a large reversible capacity of 144 mAh g-1 with the energy density approaching 514 Wh kg-1 .