Stabilizing Zinc Hexacyanoferrate Cathode by Low Contents of Cs Cations for Aqueous Zn‐Ion Batteries

Abstract Exploring cathode materials with excellent electrochemical performance is crucial for developing rechargeable aqueous zinc ion batteries (RAZIBs). Zinc hexacyanoferrate (ZnHCF), a promising candidate of cathode materials for RAZIBs, suffers from severe electrochemical instability issues. This work reports using low contents of alkaline metal cations as electrolyte additives to improve the cycle performance of ZnHCF. The cations with large sizes, particularly Cs + , changes the intercalation chemistry of ZnHCF in RAZIBs. During cycling, Cs + cations co‐inserted into ZnHCF stabilize the host structure. Meanwhile, a stable phase of CsZn[Fe(CN) 6 ] forms on the ZnHCF cathode, suppressing the loss of active materials through dissolution. ZnHCF gradually converts to an electrochemically inert Zn‐rich phase during long‐term cycling in aqueous electrolyte, leading to irreversible capacity loss. Introducing Cs + in the electrolyte inhibits this conversion reaction, resulting in the extended lifespan. Owing to these advantages, the capacity retention rate of ZnHCF/Zn full batteries increases from the original 7.0 % to a high value of 54.6 % in the electrolyte containing 0.03 M of Cs 2 SO 4 after 300 cycles at 0.25 A ⋅ g −1 . This research provides an in‐depth understanding of the electrochemical behavior of ZnHCF in aqueous zinc electrolyte, beneficial for further optimizing ZnHCF and other metal hexacyanoferrates.