Effects of the volume changes and elastic-strain energies on the phase transition in the Li-Sn battery

Sn and Sn-based compounds have been attracting a great interest as promising alternative materials for commercial anodes in lithium ion batteries. In this study, the phase evolution of the Li-Sn system during the lithiated processes and the effect of the elastic-strain energies caused by volume change on the phase transition are investigated by means of first-principles calculations. Our calculated results demonstrate that the distorted Li7Sn3 crystal tends to be formed in order to decrease the elastic-strain energy. In addition, our work indicates that the whole lithiated processes under the elastically constrained condition could be classified into two steps. The first step is the two-phase equilibrium process, in which the thermodynamic driving force is large enough to facilitate the phase transition and the plateau voltage could be established. The second step is considered to be the selective equilibrium, in which the thermodynamic driving force is not enough to facilitate the nucleation of the new equilibrium phase due to the elastically constrained conditions and the plateau voltage unformed. Besides, we find that in the Li0.4Sn matrix the nucleation of the αSn is more preferential than the βSn due to the effects of the elastic-strain energies.