Combinatorial techniques have been applied to the preparation and screening of positive electrode candidates for lithium batteries. This work describes the automated parallel synthesis of 64-electrode arrays using a Packard Multiprobe II liquid handling system. A cell was constructed with a single lithium reference–counter electrode and 64, three-millimeter-diameter working electrodes containing Li x Mn2O4 active material, PVdF–HFP binder and carbon black as a conducting additive. Eight duplicate electrodes, each of eight respective compositions, were deposited on the array and the mass fraction of carbon was varied in steps from 1 to 25%. The results showed a rapid increase in capacity at the percolation limit of 3% for most cells. Some groups of nominally identical cells showed random variations in capacity, especially at low carbon loadings. The overall result is a demonstration of advantages of the combinatorial concept, which were time-saving and an improved statistical significance of the results compared with on–off experiments.