Battery and fuel cell simulations commonly assume that electrodes are macro-homogeneous and isotropic. These simulations have been used to successfully model performance, but give little insight into predicting failure. In Li-ion battery electrodes, it is understood that local tortuosity impacts charging rates, which may cause increased degradation. This report describes a novel approach to quantifying tortuosity based on a heat transfer analogy applied to X-ray microscopy data of a commercially available LiFePO4 electrode. This combination of X-ray imaging and image-based simulation reveals the microscopic performance of the electrode; notably, the tortuosity was observed to vary significantly depending on the direction considered, which suggests that tortuosity might best be quantified using vectors rather than scalars.