Voltammetric Behaviour of LMO at the Nanoscale: A Map of Reversibility and Diffusional Limitations.

Understanding and optimizing single particle rate behaviour is normally challenging in composite commercial lithium-ion electrode materials. In this regard, recent experimental research has addressed the electrochemical Li-ion intercalation in individual nanosized particles. Here, we present a thorough theoretical analysis of the Li+ intercalation voltammetric behaviour in single nano/micro-scale LiMn2 O4 (LMO) particles, incorporating realistic interactions between inserted ions. A transparent 2-dimensional zone diagram representation of kinetic-diffusional behaviour is provided that allows rapid diagnosis of the reversibility and diffusion length of the system depending on the particle geometry. We provide an Excel file where the boundary lines of the zone diagram can be rapidly recalculated by setting input values of the rate constant, k 0 and diffusion coefficient, D . The model framework elucidates the heterogeneous behaviour of nanosized particles with similar sizes but different shapes. Hence, we present here an outlook for realistic multiscale modelling of real materials.