Intercalation of Al³⁺ into Prussian Blue Analogues from Nonaqueous Electrolytes

Nonaqueous aluminum-ion batteries (AIBs) provide advantages, such as high energy density, enhanced safety, and reduced corrosion, making them ideal for advanced energy storage solutions. A key challenge faced by AIBs is the lack of suitable cathode materials for rapid Al-ion insertion /extraction. Herein, K₂Mn[Fe(CN)₆] 2H₂O (KMHCF) is innovatively chosen as a model to investigate the aluminum storage performance of Prussian blue analogues in nonaqueous AIBs. As anticipated, the KMHCF allows for reversible aluminum storage and exhibits characteristic charge/discharge plateaus. Furthermore, carbon combined highly crystalline KMHCF (HC-KMHCF@C) is synthesized through a chelator-assisted preparation method in combination with an in situ carbon compositing technique. With reduced [Fe(CN)₆]⁴⁻ defects, lower interstitial water content, and enhanced conductivity, HC-KMHCF@C exhibits a high aluminum storage capacity (146.2 mAh g⁻¹ at 0.5 A g⁻¹) and satisfactory cycling performance (maintaining 86.4 mAh g⁻¹ after 800 cycles). The electrochemical reaction mechanism of HC-KMHCF@C is investigated in detail. During the initial charge, K⁺ ions are extracted, shifting the structure from monoclinic to cubic. In subsequent cycles, reversible Al³⁺ insertion and extraction cause the structure to alternate between monoclinic and cubic phases.