Ab initio study of lithium intercalation into a graphite nanoparticle

The process of Li intercalation is fundamental to the operation of Li-ion batteries and the computational modelling of this process, as atomic resolution would be of great benefit to the rational design of improved battery materials. Towards this goal, we present an approach and workflow for the simulation of Li intercalation which uses electrostatic considerations. These considerations use the electrostatic potential found from Density Functional Theory (DFT) calculations as a guiding principle to find favourable sites for Li intercalation. We test the method on graphite-based models of anodic carbon, graphite nanoparticles. The study of nanoparticles using first-principles methods is made possible thanks to linear-scaling DFT which allows calculations on larger numbers of atoms than conventional DFT. We show how our approach can reproduce the well-known Li staging and we investigate the electronic structure of the nanoparticle obtained via atomic charges and density of states analysis. We also compute the open circuit voltages of the structures via a convex hull formalism and find reasonable agreement with experiment with respect to the degree of Li intercalation. Our approach provides a novel route to simulating the intercalation process and, combined with linear-scaling DFT, can be used to investigate intercalation in complex nanoscale electrode structures.

Automated summary

The process of Li intercalation is important for Li-ion batteries and the computational modelling of this process can help improve battery materials. In this study, an approach using electrostatic considerations for simulating Li intercalation is presented. By finding favorable sites for Li intercalation using the electrostatic potential from DFT calculations, the method is tested on graphite-based models of anodic carbon and graphite nanoparticles. The approach successfully reproduces Li staging and investigates the electronic structure of the nanoparticle. Open circuit voltages are computed and show reasonable agreement with experiment. The method provides a novel route for simulating the intercalation process and can be applied to complex nanoscale electrode structures.