A Self‐Constructed Mg2+/K+ Co‐Doped Prussian Blue with Superior Cycling Stability Enabled by Enhanced Coulombic Attraction

Prussian blue (PB) is regarded as a promising cathode for sodium‐ion batteries because of its sustainable precursor elements (e.g., Mn, Fe), easy preparation, and unique framework structure. However, the unstable structure and inherent crystal H2O restrain its practical application. For this purpose, a self‐constructed trace Mg2+/K+ co‐doped PB prepared via a sea‐water‐mediated method is proposed to address this problem. The Mg2+/K+ co‐doping in the Na sites of PB is permitted by both thermodynamics and kinetics factors when synthesized in sea water. The results reveal that the introduced Mg2+ and K+ are immovable in the PB lattices and can form stronger K‒N and Mg‒N Coulombic attraction to relieve phase transition and element dissolution. Besides, the Mg2+/K+ co‐doping can reduce defect and H2O contents. As a result, the PB prepared in sea water exhibits an extremely long cycle life (80.1% retention after 2400 cycles) and superior rate capability (90.4% capacity retention at 20 C relative to that at 0.1 C). To address its practical applications, a sodium salts recycling strategy is proposed to greatly reduce the PB production cost. This work provides a self‐constructed Mg2+/K+ co‐doped high‐performance PB at a low preparation cost for sustainable, large‐scale energy storage. A self‐constructed trace Mg2+/K+ co‐doped Prussian blue is prepared in sea water that exhibits extremely long cycling stability with 80.1% retention after 2400 cycles at 5C. The “pillar” effect of Mg2+/K+ and strong Mg‒N and K‒N Coulombic attraction well stabilize structure, and alleviate phase transform and elements dissolution. A low‐cost and sustainable route is provided by recycling Na salts.