Dual Ion Co‐Insertion Induced Spontaneous and Reversible Phase Conversion Chemistry for Unprecedented Zn²⁺ Storage

Abstract Prussian blue analogues are highly promising electrode materials due to their versatile electrochemical activity and low cost. However, they often suffer from severe structural damage caused by the Jahn–Teller distortion and dissolution of high‐spin outer metal ions, resulting in poor cycle life. Material modification and electrolyte regulation have been the common approaches to address this issue, albeit with very limited success. We report here a novel and efficient strategy to preserve structural stability by co‐inserting Co 2+ and Zn 2+ ions in KCo[Fe(CN) 6 ]. This co‐insertion induced a spontaneous and reversible phase conversion by the replacement of low‐spin inner ion (Fe 3+ ), which efficiently relieves structural damage caused by Jahn–Teller distortion and metal‐ion dissolution, leading to an outstanding Zn 2+ storage capacity and an exceptional improvement of cycle life with a capacity retention of 97.7 % over 4400 cycles at 40 C. We also demonstrated the enhancement of co‐intercalation on ion migration using a combined approach of experimental and density functional theory (DFT) calculations. This work provides an important progress to solve the cycle stability of Prussian blue analogues towards their practical application as electrode materials for aqueous batteries.