Reaction Kinetics of Germanium Nanowire Growth on Inductively Heated Copper Surfaces

This article describes the chemical kinetics of germanium nanowire growth on inductively heated copper surfaces using diphenylgermane as a precursor. Inductive heating of metal surfaces presents a simple, rapid, and contact-free method to activate the direct growth of nanowires on metal surfaces. We show the main effects of synthesis temperature, duration, precursor concentration on the morphology, and loading of the nanowire film. We describe the complex interplay of precursor degradation, nucleation, and growth in context of a multistep reaction mechanism. We studied the temporal evolution of nanowire loading and morphology to develop a kinetic model, which predicts critical thresholds that define the onset of sequential axial and radial nanowire growth modes. These results may be used to commercially scale a nanowire growth process

Simultaneous Quantification of Electron Transfer by Carbon Matrices and Functional Groups in Pyrogenic Carbon

Pyrogenic carbon contains redox-active functional groups and polyaromatic carbon matrices that are both capable of transferring electrons. Several techniques have been explored to characterize the individual electron transfer process of either functional groups or carbon matrices individually. However, simultaneous analysis of both processes remains challenging. Using an approach that employs a four-electrode configuration and dual-interface electron transfer detection, we distinguished the electron transfer by functional groups from the electron transfer by carbon matrices and simultaneously quantified their relative contribution to the total electron transfer to and from pyrogenic carbon. Results show that at low to intermediate pyrolysis temperatures (400–500 °C), redox cycling of functional groups is the major mechanism with a contribution of 100–78% to the total electron transfer; whereas at high temperatures (650–800 °C), direct electron transfer of carbon matrices dominates electron transfer with a contribution of 87–100%. Spectroscopic and diffraction analyses of pyrogenic carbon support the electrochemical measurements by showing a molecular-level structural transition from an enrichment in functional groups to an enrichment in nanosized graphene domains with increasing pyrolysis temperatures. The method described in this study provides a new analytical approach to separately quantify the relative importance of different electron transfer pathways in natural pyrogenic carbon and has potential applications for engineered carbon materials such as graphene oxides

Dynamic Hosts for High-Performance Li–S Batteries Studied by Cryogenic Transmission Electron Microscopy and in Situ X‑ray Diffraction

Developing a high-performance sulfur host is central to the commercialization and general development of lithium–sulfur batteries. Here, for the first time, we propose the concept of dynamic hosts for lithium–sulfur batteries and elucidate the mechanism through which TiS₂ acts in such a fashion, using in situ X-ray diffraction and cryogenic scanning transmission electron microscopy (cryo-STEM). A TiS₂–S composite electrode delivered a reversible capacity of 1120 mAh g^–1 at 0.3 C after 200 cycles with a capacity retention of 97.0% and capacities of 886 and 613 mAh g^–1 at 1.0 C up to 200 and 1000 cycles, respectively. Our results indicate that it is Li_<i>x</i>TiS₂ (0 < <i>x</i> ≤ 1), rather than TiS₂, that effectively traps polysulfides and catalytically decomposes Li₂S