Specifically, the interface between AM and the SE, referred to as SAM-SE, is of particular importance as it is where lithium-ion transfer occurs. A large interface area is critical for minimizing charge transfer impedance . As shown in Figure , the specific surface area between AM and SE increases with higher degrees of calendering, with Cal35% exhibiting the largest contact area. Consequently, the pore-coverage of the AM decreases, as SAM-pores reduces from 0.02 m 2 g⁻¹ for Cal0% to 0.004 m 2 g⁻¹ for Cal35%, while SAM-SE increases from 0.01 to 0.019 m 2 g⁻¹. This increase in AM-SE contact is attributed to the pressure applied during the calendering process, which reduces voids between AM particles as already observed in the volume fraction diagram (Figure ), resulting in enhanced AM-SE connectivity. The specific surface area of the AM is measured at 0.16 m 2 g⁻¹ , and the fraction of AM surface covered by SE increases from approximately 10% at Cal0% to nearly 28% at Cal35%. Although, for Cal35%, around 6% of the AM surface is still in contact with pores, 24% with CBD and 42% with other AM particles. These findings suggest that maximizing SAM-SE and minimizing residual porosity are key to fabricating highly compact electrodes with minimal porosity, thereby optimizing the electrochemical performance of calendered electrodes. Which is in line with the findings of Bielefeld et al. , who demonstrated that a cone-like microstructure where the AM and the SE are arranged into conical formations in direct contact, exhibits higher values of active interface area between AM and SE compared to stochastically generated microstructures and experimental outcomes. This enhanced active interface area contributes in a higher amount of electrochemically accessible material which determines the achievable capacity , thereby improving the overall performance in ASSBs.