Polypyrrole-Coated K₂Mn[Fe(CN)₆] Stabilizing Its Interfaces and Inhibiting Irreversible Phase Transition during the...

Prussian blue analogues (PBAs) have been considered as promising cathodes for aqueous zinc-ion batteries because of their open framework for accommodating large ions, tunable valence state, and facile synthesis. Among PBAs, potassium manganese hexacyanoferrate (KMHCF) is favored due to its high working voltage, high specific capacity, and low cost. However, it suffers from severe capacity decay and poor rate capability, which are mainly a result of poor intrinsic conductivity, irreversible phase transition, transition metal dissolution, and structural collapse during charge/discharge cycling. These issues extremely limit its practical application. In order to solve these problems, conductive polypyrrole (PPy) was used to coat KMHCF microcubes to form KMHCF@PPy composites to achieve superior rate capability and prolonged cycle life. With the PPy coating, the KMHCF@PPy composite delivers a discharge capacity of 107.6 mA h g^-1 after 100 cycles at 100 mA g^-1, and even at 500 mA g^-1 after 500 cycles, 64.2 mA h g^-1 still remained. The excellent electrochemical performance can be attributed to the effects from PPy. On the one hand, PPy supplies an effective electronic transmission network for KMHCF to enhance the electronic conductivity. On the other hand, it plays the role of a protective layer to effectively inhibit the dissolution of Mn and the phase transition during the cycling.