Operando Observation of Coupled Discontinuous-Continuous Transitions in Ion-Stabilized Intercalation Cathodes

Irreversible phase transition caused capacity fading has been considered as an obstacle for rechargeable batteries. An in-depth investigation of the irreversible phase transition is critical for understanding the reaction mechanism and developing advanced batteries. In this work, taking vanadium oxide and its alkali ion-stabilized intercalation compounds (A-V-O, A = Li, Na, K) as prototypes, utilizing operando characterizations, we discovered coupled discontinuous (interlayer)-continuous (intralayer) transitions in the stabilized multielectron intercalation cathodes. The highly ordered crystal of vanadium pentoxide irreversibly transfers to a disordered/amorphous structure after the first cycle, whereas A-V-O enables reversible discontinuous lattice transitions at the interlayer pathway for facilitating lithium diffusion. Among the A-V-O family, K-V-O, with the highest capacity retention, shows a coupled discontinuous-continuous transition, which exhibits a continuous transition and the minimum volume change at the V-O intralayer during lithium intercalation/deintercalation. These coupled discontinuous-continuous lattice transitions were captured for the first time in cathode materials. It implies that the suitable ion intercalation induced continuous intralayer transition inhibits the irreversible ion intercalation and phase transition.