Inherent emf relaxation of electrochemical cells with nanocrystalline Ag electrodes

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.