The importance of electrode shape, alongside electrode size, as key factors in controlling the reversibility or otherwise of electrochemical responses, is recognized at the microscopic level but is explored here via finite-element simulation on the macroscopic scale. Reduced overpotential is seen for concave surfaces relative to flat or convex surfaces, providing an unexplored avenue for the design and fabrication of electrodes, including composites for diverse applications where enhanced reversibility is desirable, such as in sensors and battery materials where the promotion of electrocatalytic responses is important.

Department of Chemistry and Physico chemical processes Faculty of Materials Science and Technology VSB Technical University of Ostrava 17 listopadu 2172 15 708 00 Ostrava Poruba Czech Republic

Department of Chemistry Physical and Theoretical Chemistry Laboratory Oxford University South Parks Road Oxford OX1 3QZ Great Britain

Electrochemical Innovation Lab Department of Chemical Engineering University College London London WC1E 7JE United Kingdom

Michigan Institute for Data and AI in Society University of Michigan 500 Church Street Suite 600 Ann Arbor Michigan 48109 1042 United States

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