Intercalation events visualized in single microcrystals of graphite.

The electrochemical intercalation of layered materials, particularly graphite, is fundamental to the operation of rechargeable energy-storage devices such as the lithium-ion battery and the carbon-enhanced lead-acid battery. Intercalation is thought to proceed in discrete stages, where each stage represents a specific structure and stoichiometry of the intercalant relative to the host. However, the three-dimensional structures of the stages between unintercalated and fully intercalated are not known, and the dynamics of the transitions between stages are not understood. Using optical and scanning transmission electron microscopy, we video the intercalation of single microcrystals of graphite in concentrated sulfuric acid. Here we find that intercalation charge transfer proceeds through highly variable current pulses that, although directly associated with structural changes, do not match the expectations of the classical theories. Evidently random nanoscopic defects dominate the dynamics of intercalation

Electron beam-induced current imaging with two-angstrom resolution.

An electron microscope's primary beam simultaneously ejects secondary electrons (SEs) from the sample and generates electron beam-induced currents (EBICs) in the sample. Both signals can be captured and digitized to produce images. The off-sample Everhart-Thornley detectors that are common in scanning electron microscopes (SEMs) can detect SEs with low noise and high bandwidth. However, the transimpedance amplifiers appropriate for detecting EBICs do not have such good performance, which makes accessing the benefits of EBIC imaging at high-resolution relatively more challenging. Here we report lattice-resolution imaging via detection of the EBIC produced by SE emission (SEEBIC). We use an aberration-corrected scanning transmission electron microscope (STEM), and image both microfabricated devices and standard calibration grids

Publisher Correction: Intercalation events visualized in single microcrystals of graphite.

The Peer Review File associated with this Article was updated shortly after publication to redact confidential comments to the editor

Irreversibility at macromolecular scales in the flake graphite of the lithium-ion battery anode.

Charging a commercial lithium-ion battery intercalates lithium into the graphite-based anode, creating various lithium carbide structures. Despite their economic importance, these structures and the dynamics of their charging-discharging transitions are not well-understood. We have videoed single microcrystals of high-quality, natural graphite undergoing multiple lithiation-delithiation cycles. Because the equilibrium lithium-carbide compounds corresponding to full, half, and one-third charge are gold, red, and blue respectively, video observations give direct insight into both the macromolecular structures and the kinematics of charging and discharging. We find that the transport during the first lithiation is slow and orderly, and follows the core-shell or shrinking annuli model with phase boundaries moving at constant velocities (i.e. non-diffusively). Subsequent lithiations are markedly different, showing transport that is both faster and disorderly, which indicates that the initially pristine graphite is irreversibly and considerably altered during the first cycle. In all cases deintercalation is not the time-reverse of intercalation. These findings both illustrate how lithium enters nearly defect-free host material, and highlight the differences between the idealized case and an actual, cycling graphite anode

Differential electron yield imaging with STXM

Total electron yield (TEY) imaging is an established scanning transmission X-ray microscopy (STXM) technique that gives varying contrast based on a sample's geometry, elemental composition, and electrical conductivity. However, the TEY-STXM signal is determined solely by the electrons that the beam ejects from the sample. A related technique, X-ray beam-induced current (XBIC) imaging, is sensitive to electrons and holes independently, but requires electric fields in the sample. Here we report that multi-electrode devices can be wired to produce differential electron yield (DEY) contrast, which is also independently sensitive to electrons and holes, but does not require an electric field. Depending on whether the region illuminated by the focused STXM beam is better connected to one electrode or another, the DEY-STXM contrast changes sign. DEY-STXM images thus provide a vivid map of a device's connectivity landscape, which can be key to understanding device function and failure. To demonstrate an application in the area of failure analysis, we image a 100~nm, lithographically-defined aluminum nanowire that has failed after being stressed with a large current density.Comment: 8 pages, 6 figure

Publisher Correction: Intercalation events visualized in single microcrystals of graphite

The Peer Review File associated with this Article was updated shortly after publication to redact confidential comments to the editor

Electron beam-induced current imaging with two-angstrom resolution.

An electron microscope's primary beam simultaneously ejects secondary electrons (SEs) from the sample and generates electron beam-induced currents (EBICs) in the sample. Both signals can be captured and digitized to produce images. The off-sample Everhart-Thornley detectors that are common in scanning electron microscopes (SEMs) can detect SEs with low noise and high bandwidth. However, the transimpedance amplifiers appropriate for detecting EBICs do not have such good performance, which makes accessing the benefits of EBIC imaging at high-resolution relatively more challenging. Here we report lattice-resolution imaging via detection of the EBIC produced by SE emission (SEEBIC). We use an aberration-corrected scanning transmission electron microscope (STEM), and image both microfabricated devices and standard calibration grids