Ion transport phenomena in electrode materials

Abstract

Because of the increasing demand, high-power, high-rate energy storage devices based on electrode materials have attracted immense attention. However, challenges remain to be addressed to improve the concentration-dependent kinetics of ionic diffusion and understand phase transformation, interfacial reactions, and capacitive behaviors that vary with particle morphology and scanning rates. It is valuable to understand the microscopic origins of ion transport in electrode materials. In this review, we discuss the microscopic transport phenomena and their dependence on ion concentration in the cathode materials, by comparing dozens of well-studied transition metal oxides, sulfides, and phosphates, and in the anode materials, including several carbon species and carbides. We generalize the kinetic effects on the microscopic ionic transport processes from the phenomenological points of view based on the well-studied systems. The dominant kinetic effects on ion diffusion varied with ion concentration, and the pathway- and morphology-dependent diffusion and capacitive behaviors affected by the sizes and boundaries of particles are demonstrated. The important kinetic effects on ion transport by phase transformation, transferred electrons, and water molecules are discussed. The results are expected to shed light on the microscopic limiting factors of charging/discharging rates for developing new intercalation and conversion reaction systems.