Size-, Water-, and Defect-Regulated Potassium Manganese Hexacyanoferrate with Superior Cycling Stability and Rate Capability for Low-Cost Sodium-Ion Batteries

Potassium manganese hexacyanoferrate (KMHCF) is a low-cost Prussian blue analogue (PBA) having a rigid and open framework that can accommodate large alkali ions. Herein, the synthesis of KMHCF and its application as a high-performance cathode in sodium-ion batteries (NIBs) is reported. High-quality KMHCF with low amounts of crystal water and defects and with homogeneous microstructure is obtained by controlling the nucleation and grain growth by using a high-concentration citrate solution as a precipitation medium. The obtained KMHCF exhibits superior cycling and rate performance as a NIB cathode, showing 80% capacity retention after 1000 cycles at 1 C and a high capacity of 95 mA h g⁻¹ at 20 C. Unlike conventional single-cation batteries, the hybrid NIB with KMHCF as cathode and Na as anode in Na-ion electrolyte displays three reversible plateaus that involve stepwise insertion/extraction of both K⁺ and Na⁺ in the PBA framework. In later cycling, the K⁺–Na⁺ cointercalated phase is partially converted into a cubic sodium manganese hexacyanoferrate (NaMHCF) phase due to the increasing replacement of Na⁺ for K⁺.