In Situ Atomic Force Microscopy of Lithiation and Delithiation of Silicon Nanostructures for Lithium Ion Batteries

Using electron beam lithography, amorphous Si (a-Si) nanopillars were fabricated with a height of 100 nm and diameters of 100, 200, 300, 500, and 1000 nm. The nanopillars were electrochemically cycled in a 1 M lithium trifluoromethanesulfonate in propylene carbonate electrolyte. In situ atomic force microscopy (AFM) was used to qualitatively and quantitatively examine the morphology evolution of the nanopillars including volume and height changes versus voltage in real-time. In the first cycle, an obvious hysteresis of volume change versus voltage during lithiation and delithiation was measured. The pillars did not crack in the first cycle, but a permanent volume expansion was observed. During subsequent cycles the a-Si roughened and deformed from the initial geometry, and eventually pillars with diameters >200 nm fractured. Furthermore, a degradation of mechanical properties is suggested as the 100 and 200 nm pillars were mechanically eroded by the small contact forces under the AFM probe. Ex situ scanning electron microscopy (SEM) images, combined with analysis of the damage caused by in situ AFM imaging, demonstrate that during cycling, the silicon became porous and structurally unstable compared to as-fabricated pillars. This research highlights that even nanoscale a-Si suffers irreversible mechanical damage during cycling in organic electrolytes.