Simulations of lithium-ion battery cells are usually performed with volume averaging methods that employ effective transport properties. Bruggeman's model, which is widely used to determine these effective properties, is primarily based on the volume fraction of porous electrodes. It does not consider actual particle shape, size or the topology of constituent phases; these play a crucial role in determining effective transport. In this paper, a general derivation of the effective thermal conductivity of multiphase materials, which can be correlated with these factors, is derived using the volume averaging technique. Three-dimensional finite volume meshes of fully-resolved lithium-ion battery cathode microstructures are reconstructed from scanned images. Effective volume averaged thermal conductivity is then determined from numerical analysis of thermal transport on these meshes. It is shown that the Bruggeman model for effective thermal conductivity must be recalibrated to fit the effective thermal conductivity computed from these detailed simulations. The relevance of these results to effective transport properties typically employed in electrochemical simulations is presented. Commonly used theories for effective thermal transport in composites are evaluated for comparison. Furthermore, it is shown that Bruggeman's exponents yield an important quantitative measure, the connectivity, to characterize the physical path for transport through the underlying phases. (C) The Author(s) 2015. Published by ECS.