Maximizing the Structural Stability of the Na-Rich Prussian Blue Analogue Electrode through Charge Cutoff Voltage Regulation

Prussian blue and its analogues (PB/PBAs) are promising sodium-ion battery cathode materials due to their easy synthesis and excellent discharge capacity. However, their low structural stability poses a challenge. One critical factor affecting stability is the charge cutoff voltage. Increasing this voltage can enhance lithium-ion battery capacity but may reduce cycle retention due to intensified electrode–electrolyte interface reactions. This study investigates whether this phenomenon also applies to sodium-ion batteries and proposes an optimal voltage to improve both the capacity and stability. By cycling between 3.8 and 4.2 V, the charge/discharge profiles and redox reaction intensity were analyzed. The correlation between structural stability and charge cutoff voltage was re-evaluated based on these findings. An optimal charge cutoff voltage of 4.1 V was identified, creating an additional plateau during initial charging and altering Na+ ion positioning to enhance capacity. Enhanced mobility of ions and electrons was observed through a stable solid-electrolyte interphase (SEI) formation. Ex situ X-ray diffraction (XRD) confirmed reversible phase transitions and excellent structural stability. This study underscores the strategic use of charge cutoff voltage to enhance both discharge capacity and structural stability, offering insights for advancing PB/PBA cathode materials with improved stability and capacity.