Further investigation is conducted into the mechanism of Li + diffusion using Nudged Elastic Band (NEB) calculations within the framework of periodic DFT. The focus is on the effect of interlayer spacing in a dilute limit without pillar molecules. Initially, the Li-free V2O5 structure with a d-spacing of 0.87 nm is employed to assess the diffusion mechanisms and their activation barriers. Subsequently, the diffusion mechanisms and barriers for d-spacings of 1.21 nm and 1.50 nm are examined. Three distinct diffusion pathways are identified. Diffusion pathway 1 connects two pyramidal Li + sites, each initially exhibiting a 5-fold coordination environment, with three oxygen atoms on one side and two on the opposite side of the layers (Fig. ). Note that both sites are more prominently bound (three vs. two coordinating oxygen atoms) to opposite V2O5 bilayers. As the interlayer spacing increases, the two oxygen atoms from the upper layer are no longer capable of forming bonds, reducing the coordination number from 5-fold to 3-fold, as illustrated in Fig. . In addition, the diffusion of Li + along this pathway entails traversing the interlayer space in between the V2O5 bilayers in which an effective coordination of Li + ion is no longer maintained (Fig. ). This, in turn, leads to the formation of high diffusion barriers (>1 eV), which excludes this pathway from contributing to Li + conductivity (Fig. ).