Numerical simulation is used to explore the influence of particle shape and overall porosity on the liquid phase conductivity, sigma(eff), inside porous networks, such as electrodes or separators used for lithium-ion batteries. Such battery components are often modelled by a power law, sigma(eff) = epsilon(alpha)sigma(0), which relates electrolyte bulk conductivity sigma(0) and void volume fraction epsilon via a Bruggeman exponent alpha. Frequently, a value of 1.5 is assumed for alpha. In this work, theoretical and experimental evidence is presented to show that a Bruggeman exponent of 1.5 is often not valid for real electrodes or separator materials. It is found that only idealized morphologies, based on spherical or slightly prolate (i.e. rod-type) ellipsoids, are expected to give rise to a Bruggeman law with an exponent of about 1.3. Porous networks based on other particle morphologies such as oblate (i.e. disk-type) ellipsoids or lamellar or flaky materials increase the tortuous path for ionic conductivity and result either in a significant increase of the exponent alpha, or in a complete deviation from the power law. These models imply that spherical or slightly prolate ellipsoidal particles should be preferred for batteries where high-rate performance is required and that future separators could be designed with higher ionic conductivity. (C) 2003 Elsevier Science B.V. All rights reserved.