Compressively Stressed Silicon Nanoclusters as an Antifracture Mechanism for High-Performance Lithium-Ion Battery Anodes.

Silicon has been considered a good candidate for replacing the commonly used carbon anodes for lithium-ion batteries (LIBs) due to its high specific capacity, which can be up to 11 times higher than that of carbon. However, the desirable advantage that silicon brings to battery performance is currently overshadowed by its stress-induced performance loss and high electronic resistivity. The induced stress arises from two sources, namely, the deposition process (i.e., residual stress) during fabrication and the volume expansion (i.e., mechanical stress) associated with the lithiation/delithiation process. Of the two, residual stress has largely been ignored, underestimated, or considered to have a negligible effect without any rigorous evidence being put forward. In this contribution, we produced silicon thin films having a wide range of residual stress and resistivity using a physical vapor deposition technique, magnetron sputtering. Three pairs of silicon thin-film anodes were utilized to study the effect of residual stress on the electrochemical and cyclability performance as anodes for LIBs. Each set consisted of a pair of films having essentially the same resistivity, density, thickness, and oxidation amount but distinctly different residual stresses. The comparison was evaluated by conducting charge/discharge cycling and cyclic voltammetry (CV) experiments. In contrast to the fixed belief within the literature, higher compressive residual-stress films showed better electrochemical and cycle performance compared to lower residual-stress films. The results, herein, present an informed understanding of the role that residual stress plays, which will help researchers improve the development of silicon-based thin-film anodes.