Stochastic Local Breakdown of Oxide Film on Ni from Identical-Location Imaging: One Single Site at a Time.

The electrochemical breakdown of a metal oxide film can directly affect the performance of functional electrochemical devices. However, revealing the structural insight into the breakdown sites is challenging because of heterogeneity: different breakdown sites are spatially distributed over the surface. Herein, we combine scanning electrochemical cell microscopy with identical-location microscopies to reveal the heterogeneity in the breakdown of NiO film on Ni in a site-by-site manner. Local critical breakdown potential varies by ∼500 mV, corresponding to an excess energy of 0.02-0.12 J/m 2 . Correlative composition imaging using time-of-flight secondary ion mass spectrometry shows Ni crystal grains with thinner NiO films are more resistant to breakdown. This high resistance is explained using classical nucleation theory, where the electrical energy is affected by the film thickness through the local interfacial capacitance. The correlative imaging approach overcomes the issue of heterogeneity, providing conclusive insight into the stability of the electrochemical interfaces.