Widespread acceptance for electric vehicles is deterred by (i) range anxiety and (ii) recharging time. To be competitive with conventional fuels, battery recharging time must be less than 10 min, which amounts to a very high charging rate (~6C). At such high rates (i.e., extreme fast charge, XFC), a host of anode centric issues arise, namely suboptimal charging capacity, self-heating, and irreversible plating losses. Fundamentally these observations are a result of sluggish kinetic and transport modes at the pore scale. Here in we analyze such complex physicochemical interactions for different commercial graphite electrodes (microstructures are obtained through tomography). Even though the porosity of these structures is spatially quite uniform, the pore and solid networks exhibit considerable variations, both within the sample and across electrodes. Based on these examinations, we outline the guidelines for improving the XFC response via appropriate scaling of structural features.