A combination of step potential electrochemical spectroscopy (SPECS) and electrochemical impedance spectroscopy (EIS) has been used to examine the electrochemical cycling behaviour of a well-characterized birnessite-phase manganese dioxide sample for use in electrochemical capacitors. The resistance and interfacial properties of the macroscopic electrode were found to be irreversible with cycling. However, the corresponding properties for the individual particles were more reversible, although they did show substantial hysteresis in their behaviour during cycling. This behaviour was discussed in terms of the structural, conductivity and morphological characteristics of the birnessite at different depths of discharge. (C) 2010 Elsevier Ltd. All rights reserved.