A systematic description of microscopic mechanisms is necessary to understand mass transport in solid and liquid electrolytes. From Molecular Dynamics (MD) simulations, transport properties can be computed and provide a detailed view of the molecular and ionic motions. In this work, ionic conductivity and transport numbers in electrolyte systems are computed from equilibrium and nonequilibrium MD simulations. Results from the two methods are compared with experimental results, and we discuss the significance of the frame of reference when determining and comparing transport numbers. Two ways of computing ionic conductivity from equilibrium simulations are presented: the Nernst−Einstein approximation or the Onsager coefficients. The Onsager coefficients take ionic correlations into account and are found to be more suitable for concentrated electrolytes. Main features and differences between equilibrium and nonequilibrium simulations are discussed, and some potential anomalies and critical pitfalls of using nonequilibrium molecular dynamics to determine transport properties are highlighted.

Dendrite formation on Li metal anodes hinders commercialization of more energy-dense rechargeable batteries. Here, we use the migration energy barrier (MEB) for surface transport as a descriptor for dendrite nucleation and compare Li to Mg. Density functional theory calculations show that the MEB for the hexagonal close-packed structure is 40 and 270 meV lower than that of the body-centered cubic structure for Li and Mg, respectively. This is suggested as a reason why Mg surfaces are less prone to form dendrites than Li. We show that the close-packed facets exhibit lower MEBs because of smaller changes in atomic coordination during migration and thereby less surface distortion.

Dendrite growth on the lithium metal anode still obstructs a widespread commercialization of high energy density lithium metal batteries. In this work, we investigate how the crystal structure of the...

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