Multi-Step Crystallization of Barium Carbonate: Rapid Interconversion of Amorphous and Crystalline Precursors.

The direct observation of amorphous barium carbonate (ABC), which transforms into a previously unknown barium carbonate hydrate (herewith named gortatowskite) within a few hundred milliseconds of formation, is described. In situ X-ray scattering, cryo-, and low-dose electron microscopy were used to capture the transformation of nanoparticulate ABC into gortatowskite crystals, highly anisotropic sheets that are up to 1 μm in width, yet only about 10 nm in thickness. Recrystallization of gortatowskite to witherite starts within 30 seconds.

Facet-Dependent Thermal Instability in LiCoO.

Thermal runaways triggered by the oxygen release from oxide cathode materials pose a major safety concern for widespread application of lithium ion batteries. Utilizing in situ aberration-corrected scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS) at high temperatures, we show that oxygen release from LiCoO cathode crystals is occurring at the surface of particles. We correlated this local oxygen evolution from the LiCoO structure with local phase transitions spanning from layered to spinel and then to rock salt structure upon exposure to elevated temperatures.

Stabilizing metastable tetragonal HfO using a non-hydrolytic solution-phase route: ligand exchange as a means of controlling particle size.

There has been intense interest in stabilizing the tetragonal phase of HfO since it is predicted to outperform the thermodynamically stable lower-symmetry monoclinic phase for almost every application where HfO has found use by dint of its higher dielectric constant, bandgap, and hardness. However, the monoclinic phase is much more thermodynamically stable and the tetragonal phase of HfO is generally accessible only at temperatures above 1720 °C. Classical models comparing the competing influences of bulk free energy and specific surface energy predict that the tetragonal phase of HfO ought to be stable at ultra-small dimensions below 4 nm; however, these size regimes have been difficult to access in the absence of synthetic methods that yield well-defined and monodisperse nanocrystals with precise control over size.

Atomic Origins of Monoclinic-Tetragonal (Rutile) Phase Transition in Doped VO2 Nanowires.

There has been long-standing interest in tuning the metal-insulator phase transition in vanadium dioxide (VO2) via the addition of chemical dopants. However, the underlying mechanisms by which doping elements regulate the phase transition in VO2 are poorly understood. Taking advantage of aberration-corrected scanning transmission electron microscopy, we reveal the atomistic origins by which tungsten (W) dopants influence the phase transition in single crystalline WxV1-xO2 nanowires.

Asynchronous Crystal Cell Expansion during Lithiation of K(+)-Stabilized α-MnO2.

α-MnO2 is a promising material for Li-ion batteries and has unique tunneled structure that facilitates the diffusion of Li(+). The overall electrochemical performance of α-MnO2 is determined by the tunneled structure stability during its interaction with Li(+), the mechanism of which is, however, poorly understood. In this paper, a novel tetragonal-orthorhombic-tetragonal symmetric transition during lithiation of K(+)-stabilized α-MnO2 is observed using in situ transmission electron microscopy.

Lithiation-induced shuffling of atomic stacks.

In rechargeable lithium-ion batteries, understanding the atomic-scale mechanism of Li-induced structural evolution occurring at the host electrode materials provides essential knowledge for design of new high performance electrodes. Here, we report a new crystalline-crystalline phase transition mechanism in single-crystal Zn-Sb intermetallic nanowires upon lithiation. Using in situ transmission electron microscopy, we observed that stacks of atomic planes in an intermediate hexagonal (h-)LiZnSb phase are "shuffled" to accommodate the geometrical confinement stress arising from lamellar nanodomains intercalated by lithium ions.

Thermoelectric properties of large-scale Zn3P2 nanowire assemblies.

Gram quantities of both unfunctionalized and 1,4-benzenedithiol (BDT) functionalized zinc phosphide (Zn3P2) nanowire powders, synthesized using direct reaction of zinc and phosphorus, were hot-pressed into highly dense pellets (≥98% of the theoretical density) for the determination of their thermoelectric performance. It was deduced that mechanical flexibility of the nanowires is essential for consolidating them in randomly oriented fashion into dense pellets, without making any major changes to their morphologies. Electrical and thermal transport measurements indicated that the enhanced thermoelectric performance expected of individual Zn3P2 nanowires is still retained within large-scale nanowire assemblies.

Atomic-scale observation of lithiation reaction front in nanoscale SnO2 materials.

In the present work, taking advantage of aberration-corrected scanning transmission electron microscopy, we show that the dynamic lithiation process of anode materials can be revealed in an unprecedented resolution. Atomically resolved imaging of the lithiation process in SnO2 nanowires illustrated that the movement, reaction, and generation of b = [1[overline]1[overline]1] mixed dislocations leading the lithiated stripes effectively facilitated lithium-ion insertion into the crystalline interior. The geometric phase analysis and density functional theory simulations indicated that lithium ions initial preference to diffuse along the [001] direction in the {200} planes of SnO2 nanowires introduced the lattice expansion and such dislocation behaviors.