Layered Bismuth Selenide with a Kinetics‐Enhanced Iodine Doping Strategy Toward High‐Performance Aqueous Potassium‐Ion Storage

Abstract Aqueous potassium‐ion batteries with inherent safety, high abundance, and competitive hydrated ion‐radius point to future availability in energy storage. However, the extensively studied electrodes (metal‐oxides, Prussian‐blue‐analogues, etc.) typically suffer from undesirable capacities and sluggish kinetics owing to overwhelming ion diffusion barriers. Herein, for the first time, the metal chalcogenide bismuth selenide reinforced by iodine‐doping (I‐Bi₂Se₃) is implemented for high‐performance aqueous potassium‐ion storage. The co‐intercalation mechanism of potassium‐ion with proton in I‐Bi₂Se₃ is entirely revealed by operando synchrotron X‐ray diffraction and substantial ex‐situ analysis, and the excellent interlayer diffusion kinetics in the high‐conductive host are further enhanced by iodine‐doping, as proposed by theoretic calculations. Therefore, the resulting high diffusion coefficient and low interfacial transfer resistance endow I‐Bi₂Se₃ with superior rate performance (109.2 mAh g⁻¹ at 10 A g⁻¹) and cycling stability (91% capacity retention after 1200 cycles). Employing in hybrid‐ion batteries matching zinc metal, the highest reversible aqueous potassium‐ion storage to date of 316.8 mAh g⁻¹ is demonstrated, permitting the establishment of reliable performance pouch cells. The promising aqueous potassium intercalation chemistry built in the improved metal chalcogenide is proven to be extendable to other hybrid‐ion devices, offering novel mechanistic insights and material practices for aqueous energy storage.