Understanding the Electric Double-Layer Structure, Capacitance, and Charging Dynamics

Significant progress has been made in recent years in theoretical modeling of the electric double layer (EDL), a key concept in electrochemistry important for energy storage, electrocatalysis, and multitudes of other technological applications. However, major challenges remain in understanding the microscopic details of the electrochemical interface and charging mechanisms under realistic conditions. This review delves into theoretical methods to describe the equilibrium and dynamic responses of the EDL structure and capacitance for electrochemical systems commonly deployed for capacitive energy storage. Special emphasis is given to recent advances that intend to capture the nonclassical EDL behavior such as oscillatory ion distributions, polarization of nonmetallic electrodes, charge transfer, and various forms of phase transitions in the micropores of electrodes interfacing with an organic electrolyte or ionic liquid. This comprehensive analysis highlights theoretical insights into predictable relationships between materials characteristics and electrochemical performance and offers a perspective on opportunities for further development toward rational design and optimization of electrochemical systems.