Abstract: | Novel and low‐cost rechargeable batteries are of considerable interest for application in large‐scale energy storage systems. In this context, K‐Birnessite is synthesized using a facile solid‐state reaction as a promising cathode for potassium‐ion batteries. During synthesis, an ion exchange protocol is applied to increase K content in the K‐Birnessite electrode, which results in a reversible capacity as high as 125 mAh g?1 at 0.2 C. Upon K+ exchange the reversible phase transitions are verified by in situ X‐ray diffraction (XRD) characterization. The underlying mechanism is further revealed to be the concerted K+ ion diffusion with quite low activation energies by first‐principle simulations. These new findings provide new insights into electrode process kinetics, and lay a solid foundation for material design and optimization of potassium‐ion batteries for large‐scale energy storage. |