Nonequilibrium Electrochemical Phase Maps: Beyond Butler-Volmer Kinetics

Abstract

Accurate models of electrochemical kinetics at electrode-electrolyte interfaces are crucial to understanding the high-rate behavior of energy storage devices. Phase transformation of electrodes is typically treated under equilibrium thermodynamic conditions, while realistic operation is at finite rates. Analyzing phase transformations under nonequilibrium conditions requires integrating nonlinear electrochemical kinetic models with thermodynamic models. This had only previously been demonstrated for Butler-Volmer kinetics, where it can be done analytically. In this work, we develop a software package capable of the efficient numerical inversion of rate relationships for general kinetic models. We demonstrate building nonequilibrium phase maps, including for models such as Marcus-Hush-Chidsey that require computation of an integral, and also discuss the impact of a variety of assumptions and model parameters, particularly on high-rate phase behavior. Even for a fixed set of parameters, the magnitude of the critical current can vary by more than a factor of 2 among kinetic models.