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

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.

Effects of Solute-Solvent Hydrogen Bonding on Nonaqueous Electrolyte Structure.

We investigate the source of Raman background signal commonly misidentified as fluorescence in nonaqueous electrolytes via a variety of spectroscopies (Raman, fluorescence, NMR) and find evidence of hydrogen-bonding interactions. This hydrogen bonding gives rise to broadband anharmonic vibrational modes and suggests that anions play an important and underappreciated role in the structure of nonaqueous electrolytes. Controlling electrolyte structure has important applications in advancing in operando spectroscopy measurements as well as understanding the stability of high concentration electrolytes for next-generation electrochemical energy storage devices.

Role of surface oxides in the formation of solid-electrolyte interphases at silicon electrodes for lithium-ion batteries.

Nonaqueous solvents in modern battery technologies undergo electroreduction at negative electrodes, leading to the formation of a solid-electrolyte interphase (SEI). The mechanisms and reactions leading to a stable SEI on silicon electrodes in lithium-ion batteries are still poorly understood. This lack of understanding inhibits the rational design of electrolyte additives, active material coatings, and the prediction of Li-ion battery life in general. We prepared SEI with a common nonaqueous solvent (LiPF6 in PC and in EC/DEC 1:1 by wt %) on silicon oxide and etched silicon (001) surfaces in various states of lithiation to understand the role of surface chemistry on the SEI formation mechanism and SEI structure. Anhydrous and anoxic techniques were used to prevent air and moisture contamination of prepared SEI films, allowing for more accurate characterization of SEI chemical stratification and composition by X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS) depth profiling. Additionally, multivariate statistical methods were used to better understand TOF-SIMS depth profiling studies. We conclude that the absence of native-oxide layer on silicon has a significant impact on the formation, composition, structure, and thickness of the SEI.