In this work, we have developed a zero-dimensional vanadium redox flow battery (VRFB) model which accounts for all modes of vanadium crossover and enables prediction of long-term performance of the system in a computationally-efficient manner. Using this model, the effects of membrane thickness on a 1000-cycle operation of a VRFB system have been investigated. It was observed that utilizing a thicker membrane significantly reduces the rate of capacity fade over time (up to similar to 15%) at the expense of reducing the energy efficiency (up to similar to 2%) due to increased ohmic losses. During extended cycling, the capacity of each simulated case was observed to approach an asymptote of similar to 60% relative capacity, as the concentrations in each half-cell reach a quasi-equilibrium state. Simulations also indicated that peak power density and limiting current density exhibit a similar asymptotic trend during extended cycling (i.e., an similar to 10-15% decrease in the peak power density and an similar to 20-25% decrease in the limiting current density is observed as quasi-equilibrium state is reached). (C) 2015 The Electrochemical Society. All rights reserved.