Overall, our findings clearly indicated that higher calendering degrees enhance cell performance, as they enable more homogeneous microstructure with improved percolating pathways. To identify the underlying mechanisms behind the differences in discharge curves and microstructure, we analyzed the key electrochemical kinetics that govern the system. In particular, we focused on the average reaction overpotential on AM-SE reacting interface and the SE potential. The observed decrease in average reaction overpotential (Figure ) with increasing degrees of calendering can be attributed to the enhanced contact between the AM and SE particles. The high activation overpotential 𝜂 for the Cal0% electrode, as shown in Figure , highlights the significant voltage loss required to drive the charge transfer process due to slow rection kinetics at the AM-SE interface, either from a high reaction energy barrier or low reaction area . Cal0% exhibits a much higher activation overpotential (𝜂 ) compared to Cal20% and Cal35%, primarily due to the lower active area resulting from calendering. Figure demonstrates that the active area becomes denser and forms more continuous AM-SE contact at higher degrees of calendering. This improvement is a result of the compression applied during the calendering process, which promotes more uniform contact and reduces interfacial resistance that affects reaction kinetics. A better contact reduces energy barriers for charge transfer, allowing for more efficient electrochemical reactions at the AM-SE interface. In parallel, the reduction in electrolyte potential with increased calendaring (Figure ) is largely the result of decreased ionic resistance within the SE. As calendering improves the packing density of SE particles, the ionic percolation network becomes more continuous, facilitating the movement of ions through the SE phase. This improved ionic conduction within the solid-state matrix is critical for maintaining low overpotentials during discharge and ensuring efficient energy delivery from the cathode.