On the origin of anisotropic lithiation in crystalline silicon over germanium: A first principles study

Silicon (Si) and germanium (Ge) are both recognized as a promising anode material for high-energy lithium-ion batteries. Si is abundant and best known for its superior gravimetric energy storage capacity, while Ge exhibits faster charge/discharge rates and better capacity retention. Recently, it was discovered that Si lithiation exhibits strong orientation dependence while Ge lithiation proceeds isotropically, although they have the same crystalline structure. To better understand the underlying reasons behind these distinctive differences, we examine and compare the lithiation behaviors at the Li ₄ Si/c-Si(1 1 0) and Li ₄ Ge/c-Ge(1 1 0) model systems using ab initio molecular dynamics simulations. In comparison to lithiated c-Si, where a sharp amorphous-crystalline interface remains and advances rather slowly, lithiated c-Ge tends to loose its crystallinity rapidly, resulting in a graded lithiation front of fast propagation speed. Analysis of the elastic responses and dynamics of the host Si and Ge lattices clearly demonstrate that from the beginning of the lithiation process, Ge lattice responds with more significant weakening as compared to the rigid Si lattice. Moreover, the more flexible Ge lattice is found to undergo facile atomic rearrangements during lithiation, overshadowing the original crystallographic characteristic. These unique properties of Ge thereby contribute synergistically to the rapid and isotropic lithiation.