In addition, we performed charge transport simulations to assess geometrical descriptors, as described in section 2.3. to further elucidate the relationship between microstructure and transport processes. The geometric ionic tortuosity factor (τg) for the uncalendered microstructure, illustrated in Figure , was approximately 10. This high value indicates a significant degree of complexity in the ionic transport pathways, primarily due to the inhomogeneous distribution of SE particles and the limited number of continuous ionic channels. Such a microstructure presents multiple bottlenecks for ion transport, resulting in a more tortuous path for ionic conduction , which ultimately impairs the overall ionic mobility and, consequently, the electrochemical performance of the electrode. As the degree of calendering increases, τg is reduced significantly, reaching a value of around 4 in the highly calendered electrodes. This marked decrease in tortuosity reflects the enhanced homogeneity of the SE particle distribution , as well as the creation of more continuous and accessible ionic pathways. These findings are consistent with the homogenized microstructure and lithiation observed in Figure , where the distribution of SE and AM particles becomes more uniform, leading to fewer localized bottlenecks in ion flux, as shown in the ion flux distribution in Figure . Compared to the effective ionic conductivity, the effective electronic conductivity shows less dependence on the calendering degree with 0.24 mS cm -1 for the uncalendered electrode and 0.31 mS cm -1 for the Cal35% electrode, in Figure . The observed increase in electronic conductivity with higher calendering degrees can be directly attributed to the improved contact area between the AM and CBD, as illustrated in Figure . This enhancement in contact area facilitates more effective electronic percolation throughout the electrode, ensuring that electrons can traverse the electrode more efficiently. The improvement in microstructural connectivity, ionic and electronic, is essential for optimizing charge transport and thereby the overall performance of the battery system. Our results clearly demonstrate that the combination of poor ionic connectivity and reduced electronic percolation leads to heterogeneous lithiation, as only certain regions of the electrode experience sufficient ionic and electronic flux for full lithiation to occur. This highlights the critical role of microstructural optimization, specifically through calendering, in achieving uniform charge distribution and maximizing electrochemical efficiency.