Real-time stress measurements in germanium thin film electrodes during electrochemical lithiation/delithiation cycling

An in situ study of stress evolution and mechanical behavior of germanium as a lithium-ion battery electrode material is presented. Thin films of germanium are cycled in a half-cell configuration with lithium metal foil as counter/reference electrode, with 1M LiPF₆ in ethylene carbonate, diethyl carbonate, dimethyl carbonate solution (1:1:1, wt%) as electrolyte. Real-time stress evolution in the germanium thin-film electrodes during electrochemical lithiation/ delithiation ismeasuredby monitoring the substrate curvature using the multi-beam optical sensing method. Upon lithiation a-Ge undergoes extensive plastic deformation, with a peak compressive stress reaching as high as -0.76 ± 0.05 GPa (mean ± standard deviation). The compressive stress decreases with lithium concentration reaching a value of approximately -0.3 GPa at the end of lithiation. Upon delithiation the stress quickly became tensile and follows a trend that mirrors the behavior on compressive side; the average peak tensile stress of the lithiated Ge samples was approximately 0.83 GPa. The peak tensile stress data along with the SEM analysis was used to estimate a lower bound fracture resistance of lithiated Ge, which is approximately 5.3 J/m². It was also observed that the lithiated Ge is rate sensitive, i.e., stress depends on how fast or slow the charging is carried out.