AbstractUntangling the relationship between reactions, mass transfer, and temperature within lithium-ion batteries enables approaches to mitigate thermal hot spots and slow degradation. Here, we develop an efficient physics-based three-dimensional model to simulate lock-in thermography experiments, which synchronously record the applied current, cell voltage, and surface-temperature distribution from commercial lithium iron phosphate pouch cells. We extend an earlier streamlined model based on the popular Doyle–Fuller–Newman theory, augmented by a local heat balance. The experimental data reveal significant in-plane temperature non-uniformity during battery charging and discharging, which we rationalize with a multiscale coupling between heat flow and solid-state diffusion, in particular microscopic lithium intercalation within the electrodes. Simulations are exploited to quantify properties, which we validate against a fast full-discharge experiment. Our work suggests the possibility that non-uniform thermal states could offer a window into—and a diagnostic tool for—the microscopic processes underlying battery performance and cycle life.