Real-Time Measurement of Stress and Damage Evolution during Initial Lithiation of Crystalline Silicon

Crystalline to amorphous phase transformation during initial lithiation in (100) Si wafers is studied in an electrochemical cell with Li metal as the counter and reference electrode. During initial lithiation, a moving phase boundary advances into the wafer starting from the surface facing the lithium electrode, transforming crystalline Si into amorphous LixSi. The resulting biaxial compressive stress in the amorphous layer is measured in situ, and it was observed to be ca. 0.5 GPa. High-resolution TEM images reveal a very sharp crystalline-amorphous phase boundary, with a thickness of similar to 1 nm. Upon delithiation, the stress rapidly reverses and becomes tensile, and the amorphous layer begins to deform plastically at around 0.5 GPa. With continued delithiation, the yield stress increases in magnitude, culminating in a sudden fracture of the amorphous layer into microfragments, and the cracks extend into the underlying crystalline Si.