Templated Synthesis of SiO₂ Nanotubes for Lithium-Ion Battery Applications: An In Situ (Scanning) Transmission Electron Microscopy Study

One of the weaknesses of silicon-based batteries is the rapid deterioration of the charge-storage capacity with increasing cycle numbers. Pure silicon anodes tend to suffer from poor cycling ability due to the pulverization of the crystal structure after repeated charge and discharge cycles. In this work, we present the synthesis of a hollow nanostructured SiO2 material for lithium-ion anode applications to counter this drawback. To improve the understanding of the synthesis route, the crucial synthesis step of removing the ZnO template core is shown using an in situ closed gas-cell sample holder for transmission electron microscopy. A direct visual observation of the removal of the ZnO template from the SiO2 shell is yet to be reported in the literature and is a critical step in understanding the mechanism by which these hollow nanostructures form from their core–shell precursors for future electrode material design. Using this unique technique, observation of dynamic phenomena at the individual particle scale is possible with simultaneous heating in a reactive gas environment. The electrochemical benefits of the hollow morphology are demonstrated with exceptional cycling performance, with capacity increasing with subsequent charge–discharge cycles. This demonstrates the criticality of nanostructured battery materials for the development of next-generation Li+-ion batteries

Templated Synthesis of SiO₂ Nanotubes for Lithium-Ion Battery Applications: An In Situ (Scanning) Transmission Electron Microscopy Study

One of the weaknesses of silicon-based batteries is the rapid deterioration of the charge-storage capacity with increasing cycle numbers. Pure silicon anodes tend to suffer from poor cycling ability due to the pulverization of the crystal structure after repeated charge and discharge cycles. In this work, we present the synthesis of a hollow nanostructured SiO2 material for lithium-ion anode applications to counter this drawback. To improve the understanding of the synthesis route, the crucial synthesis step of removing the ZnO template core is shown using an in situ closed gas-cell sample holder for transmission electron microscopy. A direct visual observation of the removal of the ZnO template from the SiO2 shell is yet to be reported in the literature and is a critical step in understanding the mechanism by which these hollow nanostructures form from their core–shell precursors for future electrode material design. Using this unique technique, observation of dynamic phenomena at the individual particle scale is possible with simultaneous heating in a reactive gas environment. The electrochemical benefits of the hollow morphology are demonstrated with exceptional cycling performance, with capacity increasing with subsequent charge–discharge cycles. This demonstrates the criticality of nanostructured battery materials for the development of next-generation Li+-ion batteries

Rapid Estimation of Catalyst Nanoparticle Morphology and Atomic-Coordination by High-Resolution Z‑Contrast Electron Microscopy

Heterogeneous nanoparticle catalyst development relies on an understanding of their structure–property relationships, ideally at atomic resolution and in three-dimensions. Current transmission electron microscopy techniques such as discrete tomography can provide this but require multiple images of each nanoparticle and are incompatible with samples that change under electron irradiation or with surveying large numbers of particles to gain significant statistics. Here, we make use of recent advances in quantitative dark-field scanning transmission electron microscopy to count the number atoms in each atomic column of a single image from a platinum nanoparticle. These atom-counts, along with the prior knowledge of the face-centered cubic geometry, are used to create atomistic models. An energy minimization is then used to relax the nanoparticle’s 3D structure. This rapid approach enables high-throughput statistical studies or the analysis of dynamic processes such as facet-restructuring or particle damage

Probing the dynamics of topologically protected charged ferroelectric domain walls with the electron beam at the atomic scale

Dynamic charged ferroelectric domain walls (CDWs) overturn the classical idea that our electronic circuits need to consist of fixed components of hardware.[1,2] With their own unique electronic properties and exotic functional behaviours all confined to their nanoscale width, DWs represent a completely new 2D material phase.[3-5] The most exciting aspect of CDWs in single crystals is that they can be easily created, destroyed and moved simply by an applied stimulus. The dynamic nature of CDWs gives them the edge over other novel systems and may lead to them being the next promising disruptive quantum technology. This is an area of research at its very early stages with endless possible applications. However, to harness their true potential there is a great deal of the fundamental physics yet to uncover. As the region of interest (CDW) is atomically thin and dynamic, it is essential for the physical characterisation to be at this scale spatially and time-resolved

Targeted <i>T</i>₁ Magnetic Resonance Imaging Contrast Enhancement with Extraordinarily Small CoFe₂O₄ Nanoparticles

Extraordinarily small (2.4 nm) cobalt ferrite nanoparticles (ESCIoNs) were synthesized by a one-pot thermal decomposition approach to study their potential as magnetic resonance imaging (MRI) contrast agents. Fine size control was achieved using oleylamine alone, and annular dark-field scanning transmission electron microscopy revealed highly crystalline cubic spinel particles with atomic resolution. Ligand exchange with dimercaptosuccinic acid rendered the particles stable in physiological conditions with a hydrodynamic diameter of 12 nm. The particles displayed superparamagnetic properties and a low r2/r1 ratio suitable for a T1 contrast agent. The particles were functionalized with bile acid, which improved biocompatibility by significant reduction of reactive oxygen species generation and is a first step toward liver-targeted T1 MRI. Our study demonstrates the potential of ESCIoNs as T1 MRI contrast agents