A Dual Effect Additive Modified Electrolyte Strategy to Improve the Electrochemical Performance of Zinc‐Based Prussian Blue Analogs Energy Storage Device

Prussian blue analogs (PBA) exhibit excellent potential for energy storage due to their unique three-dimensional open framework and abundant redox active sites. However, the dissolution of transition metal ions in water can compromise the structural integrity of PBAs, leading to significant issues such as low cycle life and capacity decay. To address these challenges, we proposed a dual-effect additive-modified electrolyte method to alleviate such issues, introducing sodium ferrocyanide (Na₄Fe(CN)₆) into aqueous alkaline electrolytes. It could not only capture Zn²⁺ dissolved on the surface of Na_1.86Zn_1.46[Fe(CN)₆]_0.87 (ZnHCF) electrode material during the cycling process but also conduct redox reactions on the electrode surface to provide additional capacitance. Through experiments and molecular simulation calculations, it showed that Na₄Fe(CN)₆ can restrict the movement of Zn dissolution into the electrolyte on the electrode surface. Based on this, an asymmetric supercapacitor based on ZnHCF//activated carbon was assembled with a modified electrolyte. The assembled supercapacitor displayed a specific capacitance of 1,329.65 mF cm^-2, a power density of 2,900 mW cm^-2, and an energy density of 388.28 mW h cm^-2. This study provides a new idea for the design and construction of stable and efficient PBA energy storage materials by inhibiting the leaching of transition metals in PBA.