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Insights into Electrochemical Nucleation & Growth: New Perspective from Local Electrochemistry

par Torres Morillo, Daniel
Président du jury Visart de Bocarmé, Thierry
Promoteur Ustarroz Troyano, Jon
Publication Non publié, 2025-06-30

Thèse de doctorat

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Résumé :

The electrochemical nucleation and growth (EN&G) on active surface sites is a complex and dynamic process that has garnered significant attention in both fundamental research and technological applications. However, traditional approaches often rely on macroscopic measurements that average out the intrinsic heterogeneity of electrode surfaces, limiting our understanding of site-specific dynamics. This thesis addresses this knowledge gap by introducing a localized, high-throughput approach based on Scanning Electrochemical Cell Microscopy (SECCM), complemented by co-located high-resolution microscopy and analytical modeling. This approach provides a statistical interpretation of the nucleation process: by resolving electrochemical behavior at the microscale, we demonstrate that nucleation is not governed by a single, uniform rate but rather by a distribution of site-dependent activities influenced by surface energy, structure, and conditioning. We established that this dispersion in nucleation kinetics evolves with overpotential and surface preparation, and we introduce a distribution-based framework to quantify this variability. This allows linking local activity with macroscopic responses, offering a pathway to integrate stochastic and deterministic aspects of EN&G.This research highlights the importance of acknowledging surface heterogeneities and their impact on nucleation rates and the overall electrodeposition process. It offers a renewed perspective on the role of the surface state in electrochemical phase formation and how to incorporate this information on a new framework. By correlating electrochemical descriptors with physical characteristics of metal nanoparticles, we bridge the gap between microscopic information and macroscopic outcomes. Altogether, this work contributes new perspectives and tools for understanding EN&G, shifting the focus from ensemble-averaged models to spatially resolved, data-rich analysis. The methodologies developed here lay the foundation for predictive, controllable strategies in electrochemical manufacturing, applicable to a broad range of interfacial processes, offering a new perspective on old phenomena.