Measurements of stress and fracture in germanium electrodes of lithium-ion batteries during electrochemical lithiation and delithiation

We measure stresses that develop in sputter-deposited amorphous Ge thin films during electrochemical lithiation and delithiation. Amorphous LixGe electrodes are found to flow plastically at stresses that are significantly smaller than those of their amorphous LixSi counterparts. The stress measurements allow for quantification of the elastic modulus of amorphous LixGe as a function of lithium concentration, indicating a much-reduced stiffness compared to pure Ge. Additionally, we observe that thinner films of Ge survive a cycle of lithiation and delithiation, whereas thicker films fracture. By monitoring the critical conditions for crack formation, the fracture energy is calculated using an analysis from fracture mechanics. The fracture energies are determined to be Gamma = 8.0 J m(-2) for a-Li0.3Ge and Gamma = 5.6 J m(-2) for a-Li1.6Ge. These values are similar to the fracture energy of pure Ge and are typical for brittle fracture. Despite being brittle, the ability of amorphous LixGe to flow at relatively small stresses during lithiation results in an enhanced ability of Ge electrodes to endure electrochemical cycling without fracture. (C) 2015 Elsevier B.V. All rights reserved.