Self‐Healing of Prussian Blue Analogues with Electrochemically Driven Morphological Rejuvenation

Abstract Maintaining the morphology of electrode materials with high invertibility contributes to the prolonged cyclic stability of battery systems. However, the majority of electrode materials tend to degrade during the charge–discharge process owing to the inevitable increase in entropy. Herein, a self‐healing strategy is designed to promote morphology rejuvenation in Prussian blue analogue (PBA) cathodes by cobalt doping. Experimental characterization and theoretical calculations demonstrate that a trace amount of cobalt can decelerate the crystallization process and restore the cracked areas to ensure perfect cubic structures of PBA cathodes. The electric field controls the kinetic dynamics, rather than the conventional thermodynamics, to realize the “electrochemically driven dissolution–recrystallization process” for the periodic self‐healing phenomenon. The properties of electron transportation and ion diffusion in bulk PBA are also improved by the doping strategy, thus boosting the cyclability with 4000 cycles in a diluent electrolyte. This discovery provides a new paradigm for the construction of self‐healing electrodes for cathodes.