The open circuit voltage of the electrochemical cell Ag (nano) [solid silver electrolyte] Ag (macro) is found to be inherently unstable. Even under conditions which support the morphological stability of the arrangement of nanocrystalline silver, the particles grow significantly as soon as they function as electrodes; i.e. when they are in contact with a silver electrolyte and connected electronically at the same time. The process is shown to be due to electrochemical Ostwald ripening with the interfacial transfer of Ag+ through the Ag/electrolyte interface being the rate limiting step. Its activation energy is 0.01 eV. The decay is in good agreement with modelling results. (c) 2005 Elsevier Ltd. All rights reserved.