Operando spectral imaging of the lithium ion battery's solid-electrolyte interphase.

The lithium-ion battery is currently the preferred power source for applications ranging from smart phones to electric vehicles. Imaging the chemical reactions governing its function as they happen, with nanoscale spatial resolution and chemical specificity, is a long-standing open problem. Here, we demonstrate operando spectrum imaging of a Li-ion battery anode over multiple charge-discharge cycles using electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). Using ultrathin Li-ion cells, we acquire reference EELS spectra for the various constituents of the solid-electrolyte interphase (SEI) layer and then apply these "chemical fingerprints" to high-resolution, real-space mapping of the corresponding physical structures. We observe the growth of Li and LiH dendrites in the SEI and fingerprint the SEI itself. High spatial- and spectral-resolution operando imaging of the air-sensitive liquid chemistries of the Li-ion cell opens a direct route to understanding the complex, dynamic mechanisms that affect battery safety, capacity, and lifetime.

Development of Facile and Versatile Platinum Drug Delivering Silicasome Nanocarriers for Efficient Pancreatic Cancer Chemo-Immunotherapy.

In this study a mesoporous silica nanoparticle (MSNP) based platform is developed for high-dose loading of a range of activated platinum (Pt) chemo agents that can be attached to the porous interior through the use of electrostatic and coordination chemistry under weak-basic pH conditions. In addition to the design feature for improving drug delivery, the MSNP can also be encapsulated in a coated lipid bilayer (silicasome), to improve the colloidal stability after intravenous (IV) injection. Improved pharmacokinetics and intratumor delivery of encapsulated activated oxaliplatin (1,2-diamminocyclohexane platinum(II) (DACHPt)) over free drug in an orthotopic Kras-derived pancreatic cancer (PDAC) model is demonstrated. Not only does IV injection of the DACHPt silicasome provide more efficacious cytotoxic tumor cell killing, but can also demonstrate that chemotherapy-induced cell death is accompanied by the features of immunogenic cell death (ICD) as well as a dramatic reduction in bone marrow toxicity. The added ICD features are reflected by calreticulin and high-mobility group box 1 expression, along with increased CD8+ /FoxP3+ T-cell ratios and evidence of perforin and granzyme B release at the tumor site. Subsequent performance of a survival experiment, demonstrates that the DACHPt silicasome generates a significant improvement in survival outcome, which can be extended by delayed administration of the anti-PD-1 antibody.

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.

Electron-Transparent Thermoelectric Coolers Demonstrated with Nanoparticle and Condensation Thermometry.

More efficient thermoelectric devices would revolutionize refrigeration and energy production, and low-dimensional thermoelectric materials are predicted to be more efficient than their bulk counterparts. But nanoscale thermoelectric devices generate thermal gradients on length scales that are too small to resolve with traditional thermometry methods. Here we fabricate, using single-crystal bismuth telluride (Bi2Te3) and antimony/bismuth telluride (Sb2-xBixTe3) flakes exfoliated from commercially available bulk materials, functional thermoelectric coolers (TECs) that are only 100 nm thick. These devices are the smallest TECs ever demonstrated by a factor of 104. After depositing indium nanoparticles to serve as nanothermometers, we measure the heating and cooling produced by the devices with plasmon energy expansion thermometry (PEET), a high-spatial-resolution, transmission electron microscopy (TEM)-based thermometry technique, demonstrating a ΔT = -21 ± 4 K from room temperature. We also establish proof-of-concept for condensation thermometry, a quantitative temperature-change mapping technique with a spatial precision of ≲300 nm.

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.

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.

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.