Thermodynamically stable lithium silicides and germanides from density-functional theory calculations

Abstract: Density-functional-theory (DFT) calculations have been performed on the Li-Si and Li-Ge systems. Lithiated Si and Ge, including their metastable phases, play an important technological r^ole as Li-ion battery (LIB) anodes. The calculations comprise structural optimisations on crystal structures obtained by swapping atomic species to Li-Si and Li-Ge from the X-Y structures in the International Crystal Structure Database, where X={Li,Na,K,Rb,Cs} and Y={Si,Ge,Sn,Pb}. To complement this at various Li-Si and Li-Ge stoichiometries, ab initio random structure searching (AIRSS) was also performed. Between the ground-state stoichiometries, including the recently found Li${17}$Si${4}$ phase, the average voltages were calculated, indicating that germanium may be a safer alternative to silicon anodes in LIB, due to its higher lithium insertion voltage. Calculations predict high-density Li$1$Si$_1$ and Li$_1$Ge$_1$ $P4/mmm$ layered phases which become the ground state above 2.5 and 5 GPa respectively and reveal silicon and germanium's propensity to form dumbbells in the Li$_x$Si, $x=2.33-3.25$ stoichiometry range. DFT predicts the stability of the Li${11}$Ge$6$ $Cmmm$, Li${12}$Ge$7$ $Pnma$ and Li$_7$Ge$_3$ $P32_12$ phases and several new Li-Ge compounds, with stoichiometries Li$_5$Ge$_2$, Li${13}$Ge$5$, Li$_8$Ge$_3$ and Li${13}$Ge$_4$.