Our analysis of the electrochemical performance showed that the surface contact area is a key geometric factor in the electrode microstructure. A larger contact area between the AM and SE, resulting from the calendering process, significantly reduces ion flux bottlenecks and minimizes localized ion concentrations. We also quantified the ionic geometrical tortuosity, as well as the electrode's electronic conductivity, under different calendering conditions. These findings revealed that more compact electrode microstructures, achieved through higher degrees of calendering, shorten the pathways for charge transport, increase the number of conductive paths, and lead to more uniform lithiation throughout the cathode. The improvement of electrochemical performance with calendaring is, thereby, explained by the increasing number of percolating pathways resulted from larger the contact area between AM-SE and AM-CBD. Additionally, the heterogeneities in the state of lithiation of AM and bottlenecks in the uncalendered electrode microstructure further confirm the benefits of calendering.