Overall, the study reveals that increasing the interlayer spacing introduces a complex interplay between bond distance and coordination environments, affecting the diffusion barriers and mechanisms. Diffusion pathways traversing the interlayer space are hindered by severe undercoordination, while an alternative surface-like diffusion mechanism with low activation barriers becomes activated. This new mechanism is characterized by minimal site preference for initial, final, and intermediate sites, leading to lower activation barriers, which has implications for improving Li + conductivity in similar layered materials.