Experimental characterization of electrode microstructure continues to pose interest to the scientific community. Such imaging studies provide information about the arrangement of different constituting phases – a static information. On the other hand, correlation among electrode microstructure and system dynamics (e.g., cell performance) is still quite elusive. Specifically, how microstructural arrangement affects pore-scale transition events like intercalation and ionic transport is poorly understood, mostly since in operando experiments probing system dynamics are challenging. The present work attempts to elucidate this connection using direct numerical simulation of electrochemical transitions. An often overlooked concept in electrode performance is particle geometry. Tomography revealed particle geometries are used to study resulting electrochemical complexations during electrode operation (charge and discharge). Additionally, presence of secondary phase (binder at anode, while carbon-binder domains at cathode) gives rise to partial blockage of electrode electrolyte interface. Implications of this particle surface heterogeneity are also explored for different secondary phase arrangements. Particle morphology and heterogeneity jointly define the maximum particle utilization and in turn finite rate capacity. Interestingly C-rate dependence of (dimensionless) lithium intercalation map also changes qualitatively with particle morphology and surface heterogeneity, thus revealing the importance of accurate characterization of particle scale geometrical features.