This study presents a thermal model, derived from first principles, for electric double layer capacitors (EDLCs) with multiple ion species and/or asymmetric electrolytes. It accounts for both irreversible and reversible heat generation rates resulting from the transient electrodiffusion, of ions within the electrolyte. Detailed numerical simulations of EDLCs with planar electrodes and binary and asymmetric electrolytes were performed under galvanostatic cycling. The irreversible Joule heating decreased with increasing valency and/or diffusion coefficient of either ion. The local reversible heat generation rate near a given electrode was determined by the properties of the counterion. It increased with increasing counterion valency and/or decreasing counterion diameter. As a result, the electrode with the counterion of smaller diameter and/or larger valency experienced significantly larger temperature oscillations during galvanostatic cycling than the opposite electrode. In general, EDLC electrolytes featuring ions with large valency and/or small diameter produce large capacitance but also large reversible heating. The present study suggests that EDLC electrolytes should feature large bulk ion concentrations and at least one ion with a large diffusion coefficient to minimize both irreversible and reversible heating. (C) 2014 Elsevier B.V. All rights reserved.