Entropy and Electronic Structure Modulation of a Prussian Blue Analogue Cathode with Suppressed Phase Evolution for Potassium-Ion Batteries.

Abstract

Severe structural evolution and high content of [Fe(CN)₆]^4- defects drastically deteriorate K-ion storage performances of Prussian blue-based cathodes. Herein, a potassium manganese iron copper hexacyanoferrate (KFe_2/3Mn_1/6Cu_1/6HCF), with suppressed anionic vacancies, eliminated band gap, and low K-ion diffusion barrier, is regarded as a cathode for potassium-ion batteries. The entropy stabilization effect and robust Cu-N bond induced by the inert Cu-ion with large electronegativity boost KFe_2/3Mn_1/6Cu_1/6HCF to exhibit great phase state stability, thus inhibiting the structural transition of monoclinic ↔ cubic. Hence, KFe_2/3Mn_1/6Cu_1/6HCF undergoes a zero-stress solid-solution reaction mechanism, where Fe and Mn serve as dual active sites for charge compensation. Consequently, KFe_2/3Mn_1/6Cu_1/6HCF displays a high reversible capacity of 127.5 mAh·g^-1 with an energy density of 469.2 Wh·kg^-1 at 10 mA·g^-1 and superior cyclic stability with a high retention of 90.7% over 100 cycles. A high-energy-density K-ion full battery is assembled, contributing an ultralong lifetime over 1000 cycles with a low-capacity fading rate of 0.038% per cycle.