Structural Engineering of Prussian Blue Analogues Enabling All-Climate and Ultralong Cycling Sodium-Ion Batteries

The development of cost-efficient, long-lifespan, and all-climate sodium-ion batteries is of great importance for advancing large-scale energy storage but is plagued by the lack of suitable cathode materials. Here, we report low-cost Na-rich Mn-based Prussian blue analogues with superior rate capability and ultralong cycling stability over 10,000 cycles via structural optimization with electrochemically inert Ni atoms. Their thermal stability, all-climate properties, and potential in full cells are investigated in detail. Multiple in situ characterizations reveal that the outstanding performances benefit from their highly reversible three-phase transformations and trimetal (Mn–Ni–Fe) synergistic effects. In addition, a high sodium diffusion coefficient and a low volume distortion of 2.3% are observed through in situ transmission electron microscopy and first-principles calculations. Our results provide insights into the structural engineering of Prussian blue analogues for advanced sodium-ion batteries in large-scale energy storage applications.