Properties of lithium-ion battery electrodes relate to the complex microstructure that develops during solvent removal. We use cryogenic scanning electron microscopy in combination with broad ion beam slope-cutting (Cryo-BIB-SEM) for the ex-situ imaging of film formation in battery electrodes. Drying of anode films is quenched by cryo-preservation in slushy nitrogen at systematically increasing drying times, followed by SEM imaging under cryogenic conditions. Energy dispersive x-ray spectroscopy (EDS) and image processing of segmented cross-sections are used to analyze the development of component gradients with time. We find electrode films to shrink homogeneously and not in a top-down consolidation process as previously hypothesized. Binder gradients evolve in the liquid phase and initiate solvent diffusion from the bulk to the surface, thereby dragging binder towards the surface. Capillary transport is identified as a fundamental process that directly impacts drying kinetics and binder distribution.