Vacancies‐regulated Prussian Blue Analogues through Precipitation Conversion for Cathodes in Sodium‐ion Batteries with Energy Densities over 500 Wh/kg

Prussian blue analogues (PBAs) have been widely applied in many fields, especially as cathode materials of sodium-ion batteries on account of their low cost and open framework for fast ions transport. However, the capacity of reported PBAs has a great distance from its theoretical value. Herein, we proposed that [Fe(CN)6 ] vacancies are crucial point for the high specific capacity for the first time. The [Fe(CN)6 ] vacancies may create net electrons and reduce obstacles to ionic transport, which is conducive to rate performance of PBAs by increasing electronic and ionic conductivity to some extent. As a proof of concept, a series of PBAs have been prepared by co-precipitation method. And then, a novel precipitation conversion method has been designed, by which unique PBAs with a specific quantity of [Fe(CN)6 ] vacancies was successfully synthesized. Remarkably, the as-prepared PBAs possessing hierarchical hollow morphology have reached a unprecedent level of high capacity (168 mAh g-1 at 25 mA g-1 , close to PBAs' theoretical capacity 170 mAh g-1 ), high rate performance (90 mAh g-1 at 5 A g-1 ), and high energy density (over 500 Wh kg-1 ).