Homeostatic Solid Solution in Layered Transition-Metal Oxide Cathodes of Sodium-Ion Batteries

Abstract

Two-phase transformation reaction is ubiquitous in solid-state electrochemistry; however, it usually involves inferior structure rearrangement upon extraction and insertion of large-sized Na⁺, thus leading to severe local strain, cracks, and capacity decay in sodium-ion batteries (SIBs). Here, a homeostatic solid solution reaction is reported in the layered cathode material P'2-Na_0.653Ni_0.081Mn_0.799Ti_0.120O₂ during sodiation and desodiation. It is induced by the synergistic incorporation of Ni and Ti for the reinforced O(2p)-Mn(3d-e_g*) hybridization, which leads to mitigated Jahn-Teller distortion of MnO₆ octahedra, contracted transition-metal oxide slabs, and enlarged Na layer spacings. The thermodynamically favorable solid solution pathway rewards the SIBs with excellent cycling stability (87.2% capacity retention after 500 cycles) and rate performance (100.5 mA h g^-1 at 2500 mA g^-1). The demonstrated reaction pathway will open a new avenue for rational designing of cathode materials for SIBs and beyond.