Volume 3, Issue 10 -

Electrodes are, in combination with electrolytes and the active, reacting materials the function-giving materials in electrochemical energy storage devices. They are responsible for the transfer of electrons and provide the surface at which the electrochemical reactions take place. Those electrochemical reactions span the potential difference which drives the battery. We present a crystallographically inspired systematisation of all electrodes found in electrochemical storages that comprise inert and reactive electrodes, subdivided in active and passive electrodes, and solvation, mixed crystal, and phase transition electrodes, respectively. After the description of all electrode types we present a concise summary of battery chemistries and the applied electrode types.

The synthesis of metallic nanoparticles has been of long standing interest, primarily induced by their novel and unique properties that differ considerably from bulk materials. Despite various methods have been developed, it is still a challenge to produce high-quality metallic nanoparticles with controllable properties in a simple, cost-effective and environmentally benign manner. However, the development of the microplasma-assisted technology can bring an answer to this formidable challenge. In the present work, four main microplasma configurations used for metallic synthesis of metallic nanoparticles are reviewed.  These are  hollow-electrode microdischarges, microplasma jets with external electrodes, microplasma jets with consumable electrodes and plasma–liquid systems. The state of the art characterization methodologies and diagnostic techniques for in situ microplasma-assisted precursor dissociation as well as ex situ  metallic nanoparticles analysis is also summarized. Further, a broad category of representative examples of microplasma-induced metallic nanoparticle fabrication is presented, together with the discussion of possible synthesis mechanisms. This is followed by a brief introduction to related safety considerations. Finally, the future perspectives, associated challenges and feasible solutions for scale-up of this technique are pointed out. Graphical Abstract :

Graphene-like nanostructures, solely or in combination with redox active compounds, are an important component of battery electrodes. Design of effective electrode materials requires a deep understanding of electrochemical reactions occurring at graphene surfaces. The methods of X-ray photoelectron spectroscopy (XPS) are very helpful in such research, providing the composition of studied samples and electronic state of individual elements. In this chapter, we demonstrate advantages of XPS for monitoring of chemical vapor deposition graphene growth and lithium penetration under graphene layers, disclosing of interactions with metals and interface states.

The performance characteristics of modern electrochemical energy storage devices are largely determined by the processes occurring at charge separation interfaces, as well as by the evolution of the structure, composition and chemistry of electrodes and electrolytes. The paper reviews the principal applications of neutron scattering techniques in structural studies of electrode materials and electrochemical interfaces in the course of their operation (operando mode) with an accent to Li-ion batteries. The high penetrating power of thermal neutrons makes it possible to study complex systems that are the closest to real electrochemical cells. The recent progress and future tasks in the development of the neutron scattering methods (diffraction, reflectometry, small-angle scattering) for various types of electrodes/interfaces in Li energy storage devices are discussed.

In this article, synthetic strategies and characterization methodologies of atomically precise gold clusters have been summarized. The typical and effective synthetic strategies including a systematic “size-focusing” methodology has been developed for attaining atomically precise gold clusters with size control. Another universal synthetic methodology is ligand exchange-induced size/structure transformation (LEIST) based on from one stable size to another. These two methodologies have largely expanded the “universe” of atomically precise gold clusters. Elite of typical synthetic case studies of ligand protected gold clusters are presented. Important characterization techniques of these atomically precise gold clusters also are included. The identification and characterization of gold clusters have been achieved in terms of nuclearity (size), molecular formulation, and geometrical structures by the combination of these techniques. The determination of gold cluster structure based on single crystals is of paramount importance in understanding the relationship of structure–property. The criterion and selection of these typical gold clusters are all “strictly” atomically precise that all have been determined ubiquitously by single crystal diffraction. These related crystallographic data are retrieved from Cambridge Crystallographic Data Centre (CCDC) up to 30th November 2017. Meanwhile, the cutting edge and other important characterization methodologies including electron diffraction (ED), extended X-ray absorption fine structure (EXFAS), and synchrotron sources are briefly reviewed. The new techniques hold the promise of pushing the limits of crystallization of gold clusters. This article is not just an exhaustive and up to date review, generally summarized synthetic strategies, but also a practical guide regarding gold cluster synthesis. We called it a “Cookbook” of ligand protected gold clusters, including synthetic recipes and characterization details. Graphical Abstract :

In this review paper, we provide a short overview of the application of magnetic resonance techniques in electrochemical studies. Brief theoretical descriptions, sensitivity aspects, challenges and new opportunities of nuclear magnetic resonance and electron paramagnetic resonance have been presented here. Particular attention will be paid to the studies using ex situ and in situ methodologies and their combination to address the questions concerning the intrinsic structures and the structural transformations, ionic mobility and interfacial interactions in the energy storage and energy conversion systems. In addition, theoretical approaches to support the experimental NMR observables as well as magnetic resonance imaging have been discussed in the context of improving electrochemical performance, cycling stability and safety of batteries.

Using four distinct configurations of the boron-vacancy (BV) complex in silicon, we investigate the experimentally observed defect metastability of the BV complex in silicon using the HSE06 hybrid functional within the density functional theory formalism. We identify the experimentally observed metastable configurations of the defect complex when the substitutional boron is in the nearest neighbor position with respect to silicon vacancy and when the two defects are in the next (second) nearest neighbor position with respect to each other. The next (second) nearest neighbor position consists of two configurations that almost degenerate with C 1 and C 1 h symmetry.

Homogeneously catalyzed hydrogenation/dehydrogenation reactions represent not only one of the most synthetically important chemical transformations, but also a promising way to renewably utilize the hydrogen energy. In order to rationally design efficient homogeneous catalysts for hydrogenations/dehydrogenations, it is of fundamental importance to understand their reaction mechanisms in detail. With this aim in mind, we herein provide a brief overview of the mechanistic understanding and related catalyst design strategies. Hydrogenations and dehydrogenations represent the reverse process of each other, and involve the activation/release of H 2 and the insertion/elimination of hydride as major steps. The mechanisms discussed in this chapter include the cooperation (bifunctional) mechanism and the non-cooperation mechanisms. Non-cooperation mechanisms usually involve single-site transition metal (TM) catalysts or transition metal hydride (TM-H) catalysts. Cooperation mechanisms usually operate in the state-of-the-art bifunctional catalysts, including Lewis-base/transition-metal (LB-TM) catalysts, Lewis-acid/transition-metal (LA-TM) catalysts, Lewis-acid/Lewis-base (LA-LB; the so-called frustrated Lewis pairs - FLPs) catalysts, newly developed ambiphilic catalysts, and bimetallic transition-metal/transition-metal (TM-TM) catalysts. The influence of the ligands, the electronic structure of the metal, and proton shuttle on the reaction mechanism are also discussed to improve the understanding of the factors that can govern mechanistic preferences. The content presented in this chapter should both inspire experimental and theoretical chemists concerned with homogeneously catalyzed hydrogenation and dehydrogenation reactions, and provide valuable information for future catalyst design.

Palladium (Pd) has attracted substantial academic interest due to its remarkable properties and extensive applications in many industrial processes and commercial devices. The development of Pd nanocrystals (NCs) would contribute to reduce overall precious metal loadings, and allow the efficient utilization of energy at lower economic costs. Furthermore, some of the important properties of Pd NCs can be substantially enhanced by rational designing and tight controlling of both size and shape. In this review, we have summarized the state-of-the-art research progress in the shape and size-controlled synthesis of noble-metal Pd NCs, which is based on the wet-chemical synthesis. Pd NCs have been categorized into five types: (1) single-crystalline Pd nano-polyhedra with well-defined low-index facets (e.g. {100}, {111} and {110}); (2) single-crystalline Pd nano polyhedra with well-defined high-index facets, such as Pd tetrahexahedra with {hk0} facets; (3) Pd NCs with cyclic penta-twinned structure, including icosahedra and decahedra; (4) monodisperse spherical Pd nanoparticles; (5) typical anisotropic Pd NCs, such as nanoframes, nanoplate, nanorods/wires. The synthetic approach and growth mechanisms of these types of Pd NCs are highlighted. The key factors that control the structures, including shapes (surface structures), twin structures, single-crystal nanostructures, and sizes are carefully elucidated. We also introduce the detailed characterization tools for analysis of Pd NCs with a specific type. The challenges faced and perspectives on this promising field are also briefly discussed. We believe that the detailed studies on the growth mechanisms of NCs provide a powerful guideline to the rational design and synthesis of noble-metal NCs with enhanced properties. Graphical Abstract :