Monitoring Volumetric Changes in Silicon Thin-Film Anodes through In Situ Optical Diffraction Microscopy.

Abstract

A high-resolution in situ spectroelectrochemical optical diffraction experiment has been developed to understand the volume expansion/contraction process of amorphous silicon (a-Si) thin-film anodes. Electrodes consisting of 1D transmissive gratings of silicon have been produced through photolithographic methods. After glovebox assembly in a home-built Teflon cell, monitoring of the diffraction efficiency of these gratings during the lithiation/delithiation process is performed using an optical microscope equipped with a Bertrand lens. When the diffraction efficiency along with optical constants obtained from in situ spectroscopic ellipsometry is utilized, volume changes of the active materials can be deduced. Unlike transmission electron microscopy and atomic force microscopy characterization methods of observing silicon's volume expansion, this experiment allows for real-time monitoring of the volume change at charge/discharge cycles greater than just the first few along with an experimental environment that directly mimics that of a real battery. This technique shows promising results that provide needed insight into understanding the lithium alloying reaction and subsequent induced capacity fade during the cycling of alloying anodes in lithium-ion batteries.