Abstract
This work systematically explores the core foundational mechanisms and kinetics of the metal electrocrystallization processes at the anodes of the most studied rechargeable batteries relying on electrodeposition. The analysis requires a consideration of the theoretical principles of electrochemical phase formation, including thermodynamic and kinetic models, with a strong focus on the underlying mechanisms of nucleation and growth. The review provides a comprehensive comparison of alkali and multivalent metals, highlighting their distinct electrocrystallization behaviors in the context of metal anode batteries. Specific focus is placed on metal electrodeposition on foreign substrates, which is relevant to anode-free rechargeable batteries. In these systems, precise control of nucleation and growth is essential, as homogeneous surface morphology is important for avoiding localized crystal growth and the formation of hazardous dendrites that can cause short-circuiting. Special attention is paid to the critical analysis of electrochemical crystal growth with an emphasis on the conditions and mechanisms of developing dendritic and uniform surface morphologies. The aspects of multiple nucleation in the studied systems are discussed. This work will assist electrochemists, material scientists and development engineers to identify optimal operating parameters and conditions for designing batteries based on electroplating. The interrelation between nucleation and growth and battery performance is demonstrated by representative examples.