Stochastic and cooperative processes in far from equilibrium mesoscopic electrochemical systems

Despite the growing interest in understanding the properties of microstructured electrochemical systems, their cooperative behavior as well as the impact of noise on such small systems in the presence of a nonlinear reaction kinetics is a widely unexplored topic. In this short review, the stochastic and cooperative processes occurring during a bistable electrochemical reaction are presented going from systems composed of a single entity to an ensemble of coupled electrodes or particles. Striking parallels can be established between the behavior of two important bistable electrochemical systems: the CO electrooxidation on Pt electrodes and the intercalation of Li in phase-separating LiFePO₄ battery materials. Understanding the cooperative phenomena emerging in such nonlinear microstructured electrochemical systems is critical for the optimization of their performances.