Complex, electrochemically driven transport processes form the basis of electrochemical energy storage devices. The direct imaging of electrochemical processes at high spatial resolution and within their native liquid electrolyte would significantly enhance our understanding of device functionality, but has remained elusive. In this work we use a recently developed liquid cell for in situ electrochemical transmission electron microscopy to obtain insight into the electrolyte decomposition mechanisms and kinetics in lithium-ion (Li-ion) batteries by characterizing the dynamics of solid electrolyte interphase (SEI) formation and evolution. Here we are able to visualize the detailed structure of the SEI that forms locally at the electrode/electrolyte interface during lithium intercalation into natural graphite from an organic Li-ion battery electrolyte. We quantify the SEI growth kinetics and observe the dynamic self-healing nature of the SEI with changes in cell potential.

Insight into dynamic electrochemical processes can be obtained with in situ electrochemical-scanning/transmission electron microscopy (ec-S/TEM), a technique that utilizes microfluidic electrochemical cells to characterize electrochemical processes with S/TEM imaging, diffraction, or spectroscopy. The microfluidic electrochemical cell is composed of microfabricated devices with glassy carbon and platinum microband electrodes in a three-electrode cell configuration. To establish the validity of this method for quantitative in situ electrochemistry research, cyclic voltammetry (CV), choronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) were performed using a standard one electron transfer redox couple [Fe(CN)6]3−/4−-based electrolyte. Established relationships of the electrode geometry and microfluidic conditions were fitted with CV and chronoamperometic measurements of analyte diffusion coefficients and were found to agree with well-accepted values that are on the order of 10−5 cm2/s. Influence of the electron beam on electrochemical measurements was found to be negligible during CV scans where the current profile varied only within a few nA with the electron beam on and off, which is well within the hysteresis between multiple CV scans. The combination of experimental results provides a validation that quantitative electrochemistry experiments can be performed with these small-scale microfluidic electrochemical cells provided that accurate geometrical electrode configurations, diffusion boundary layers, and microfluidic conditions are accounted for.

Thin coatings deposited on ceramic fibers prior to densification employing chemical vapor infiltration techniques have been used to limit fiber-matrix bonding. This has resulted in improvements in strength and toughness at room and elevated temperatures in Nicalon® fiber-reinforced/SiC matrix composites. The properties of the fiber-matrix interface in fiber-reinforced ceramic composites have been examined utilizing an indentation method in which a standard microhardness indentor is used to push on fibers embedded in the ceramic matrix. Compositions and microstructures at the interface have been characterized employing analytical electton microscopy. Correlations between interfacial phenomena and observed mechanical behavior have been made.

Extended abstract of a paper presented at Microscopy and Microanalysis 2004 in Savannah, Georgia, USA, August 1–5, 2004.

Extended abstract of a paper presented at Microscopy and Microanalysis 2004 in Savannah, Georgia, USA, August 1–5, 2004.

Silicon-incorporated amorphous hydrocarbon (Si-aC:H) films with varying Si contents were deposited onto a Ti interlayer on Si and steel substrates by reactive sputtering in an unbalanced magnetron sputtering system. The objective of this study was to measure and relate the structural, chemical, and mechanical properties of these Si-aC:H films. Transmission electron microscopy revealed that the Si-aC:H phase is amorphous and TiC exists at the Si-aC:H/Ti phase boundary for all compositions. Mechanical properties such as hardness, indentation modulus, and intrinsic stress decreased with increasing Si and H content in the films, for Si/C ≥ 0.04. XPS measurements suggested that this is most likely due to the decreasing presence of a C-C sp3 interlinked network, accompanied by an increase in C-H and Si-H bonds. This conclusion was supported by radial distribution functions obtained using extended electron energy-loss fine structure analysis (EXELFS).

Crystalline MoS2 films were deposited on Si and graphite substrates using MoF6 and H2S as precursors. The crystal orientation and near-interface structure of the MoS2 films were studied using transmission electron microscopy. In general, the preferred orientation of the (002) basal planes of the MoS2 films with respect to the substrate surface changed from parallel to perpendicular with increased deposition temperature from 320 to 430 °C. At 430 °C, the basal planes were primarily oriented perpendicular to the Si substrate, except for the presence of a ∼5 nm interface region in which the basal planes were oriented in the parallel direction. The formation of this transitional region was also observed on the graphite substrate.