Electrocatalysis in Alkaline Media and Alkaline Membrane-Based Energy Technologies.

Hydrogen energy-based electrochemical energy conversion technologies offer the promise of enabling a transition of the global energy landscape from fossil fuels to renewable energy. Here, we present a comprehensive review of the fundamentals of electrocatalysis in alkaline media and applications in alkaline-based energy technologies, particularly alkaline fuel cells and water electrolyzers. Anion exchange (alkaline) membrane fuel cells (AEMFCs) enable the use of nonprecious electrocatalysts for the sluggish oxygen reduction reaction (ORR), relative to proton exchange membrane fuel cells (PEMFCs), which require Pt-based electrocatalysts. However, the hydrogen oxidation reaction (HOR) kinetics is significantly slower in alkaline media than in acidic media. Understanding these phenomena requires applying theoretical and experimental methods to unravel molecular-level thermodynamics and kinetics of hydrogen and oxygen electrocatalysis and, particularly, the proton-coupled electron transfer (PCET) process that takes place in a proton-deficient alkaline media. Extensive electrochemical and spectroscopic studies, on single-crystal Pt and metal oxides, have contributed to the development of activity descriptors, as well as the identification of the nature of active sites, and the rate-determining steps of the HOR and ORR. Among these, the structure and reactivity of interfacial water serve as key potential and pH-dependent kinetic factors that are helping elucidate the origins of the HOR and ORR activity differences in acids and bases. Additionally, deliberately modulating and controlling catalyst-support interactions have provided valuable insights for enhancing catalyst accessibility and durability during operation. The design and synthesis of highly conductive and durable alkaline membranes/ionomers have enabled AEMFCs to reach initial performance metrics equal to or higher than those of PEMFCs. We emphasize the importance of using membrane electrode assemblies (MEAs) to integrate the often separately pursued/optimized electrocatalyst/support and membranes/ionomer components. Operando/in situ methods, at multiscales, and ab initio simulations provide a mechanistic understanding of electron, ion, and mass transport at catalyst/ionomer/membrane interfaces and the necessary guidance to achieve fuel cell operation in air over thousands of hours. We hope that this Review will serve as a roadmap for advancing the scientific understanding of the fundamental factors governing electrochemical energy conversion in alkaline media with the ultimate goal of achieving ultralow Pt or precious-metal-free high-performance and durable alkaline fuel cells and related technologies.

Regulating Key Variables and Visualizing Lithium Dendrite Growth: An Operando X-ray Study.

Although Li metal has long been considered to be the ideal anode material for Li rechargeable batteries, our limited understanding of the complex mechanism of Li plating has hindered the widespread deployment of Li metal anodes. Therefore, operando studies are required to unambiguously reveal the complex mechanistic steps involved. In this study, we employed synchrotron-based X-ray imaging methods to visualize the evolution of Li plating/stripping under operando and, more importantly, practical conditions for battery operation, providing detailed insights into morphology evolution during Li plating. The effects of critical battery operating parameters, including concentration of Li salts, current density, ionic strength, and various electrolytes and additives, on Li plating/stripping have been studied. The delicate interplay of these conditions on the resulting Li metal morphology has been characterized for the first time.

In Situ X-ray Absorption Spectroscopy of a Synergistic Co-Mn Oxide Catalyst for the Oxygen Reduction Reaction.

Identifying the catalytically active site(s) in the oxygen reduction reaction (ORR), under real-time electrochemical conditions, is critical to the development of fuel cells and other technologies. We have employed in situ synchrotron-based X-ray absorption spectroscopy (XAS) to investigate the synergistic interaction of a Co-Mn oxide catalyst which exhibits impressive ORR activity in alkaline fuel cells. X-ray absorption near edge structure (XANES) was used to track the dynamic structural changes of Co and Mn under both steady state (constant applied potential) and nonsteady state (potentiodynamic cyclic voltammetry, CV). Under steady state conditions, both Mn and Co valences decreased at lower potentials, indicating the conversion from Mn(III,IV) and Co(III) to Mn(II,III) and Co(II), respectively. Rapid X-ray data acquisition, combined with a slow sweep rate in CV, enabled a 3 mV resolution in the applied potential, approaching a nonsteady (potentiodynamic) state. Changes in the Co and Mn valence states were simultaneous and exhibited periodic patterns that tracked the cyclic potential sweeps. To the best of our knowledge, this represents the first study, using in situ XAS, to resolve the synergistic catalytic mechanism of a bimetallic oxide. Strategies developed/described herein can provide a promising approach to unveil the reaction mechanism for other multimetallic electrocatalysts.

Revealing the atomic ordering of binary intermetallics using in situ heating techniques at multilength scales.

Ordered intermetallic nanoparticles are promising electrocatalysts with enhanced activity and durability for the oxygen-reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs). The ordered phase is generally identified based on the existence of superlattice ordering peaks in powder X-ray diffraction (PXRD). However, after employing a widely used postsynthesis annealing treatment, we have found that claims of "ordered" catalysts were possibly/likely mixed phases of ordered intermetallics and disordered solid solutions. Here, we employed in situ heating, synchrotron-based, X-ray diffraction to quantitatively investigate the impact of a variety of annealing conditions on the degree of ordering of large ensembles of Pt3Co nanoparticles. Monte Carlo simulations suggest that Pt3Co nanoparticles have a lower order-disorder phase transition (ODPT) temperature relative to the bulk counterpart. Furthermore, we employed microscopic-level in situ heating electron microscopy to directly visualize the morphological changes and the formation of both fully and partially ordered nanoparticles at the atomic scale. In general, a higher degree of ordering leads to more active and durable electrocatalysts. The annealed Pt3Co/C with an optimal degree of ordering exhibited significantly enhanced durability, relative to the disordered counterpart, in practical membrane electrode assembly (MEA) measurements. The results highlight the importance of understanding the annealing process to maximize the degree of ordering in intermetallics to optimize electrocatalytic activity.

High-Performance Ga2O3 Anode for Lithium-Ion Batteries.

There is a great deal of interest in developing battery systems that can exhibit self-healing behavior, thus enhancing cyclability and stability. Given that gallium (Ga) is a metal that melts near room temperature, we wanted to test if it could be employed as a self-healing anode material for lithium-ion batteries (LIBs). However, Ga nanoparticles (NPs), when directly applied, tended to aggregate upon charge/discharge cycling. To address this issue, we employed carbon-coated Ga2O3 NPs as an alternative. By controlling the pH of the precursor solution, highly dispersed and ultrafine Ga2O3 NPs, embedded in carbon shells, could be synthesized through a hydrothermal carbonization method. The particle size of the Ga2O3 NPs was 2.6 nm, with an extremely narrow size distribution, as determined by high-resolution transmission electron microscopy and Brunauer-Emmett-Teller measurements. A lithium-ion battery anode based on this material exhibited stable charging and discharging, with a capacity of 721 mAh/g after 200 cycles. The high cyclability is due to not only the protective effects of the carbon shell but also the formation of Ga0 during the lithiation process, as indicated by operando X-ray absorption near-edge spectroscopy.

Direct visualization of sulfur cathodes: new insights into Li-S batteries via operando X-ray based methods.

As the need for the development of "beyond lithium" ion battery technologies continuous unabated, lithium sulfur batteries have attracted widespread attention due to their very high theoretical energy density of 2,600 Wh kg-1. However, despite much effort, the detailed reaction mechanism remains poorly understood. In this study, we have combined operando X-ray diffraction and X-ray microscopy along with X-ray tomography, to visualize the evolution of both the morphology and crystal structure of the materials during the entire battery cycling (discharging/charging) process. The dissolution and reformation of sulfur clusters is clearly observed during cycling. In addition, we demonstrate, for the first time, the critical role of current density and temperature in determining the size of both the resulting sulfur clusters and Li2S particles. This study provides new insights about promising avenues for the continued development of lithium sulfur batteries, which we believe may lead to their broad deployment and application.

SnS/C nanocomposites for high-performance sodium ion battery anodes.

Sodium-ion batteries have been considered as one of the most promising types of batteries, beyond lithium-ion batteries, for large-scale energy storage applications. However, their deployment hinges on the development of new anode materials, since it has been shown that many important anode materials employed in lithium ion batteries, such as graphite and silicon, are inadequate for sodium-ion batteries. We have simply prepared novel SnS/C nanocomposites through a top-down approach as anode materials for sodium-ion batteries. Their electrochemical performance has been significantly improved when compared to bare SnS, especially in terms of cycling stability and rate capabilities. SnS/C nanocomposites exhibit excellent capacity retention, at various current rates, and deliver capacities as high as 400 mA h g-1 even at the high current density of 800 mA g-1 (2C). Ex situ transmission electron microscopy, X-ray diffraction and operando X-ray absorption near edge structure studies have been performed in order to unravel the reaction mechanism of the SnS/C nanocomposites.

Structure of the Photo-catalytically Active Surface of SrTiO3.

A major goal of energy research is to use visible light to cleave water directly, without an applied voltage, into hydrogen and oxygen. Although SrTiO3 requires ultraviolet light, after four decades, it is still the "gold standard" for the photo-catalytic splitting of water. It is chemically robust and can carry out both hydrogen and oxygen evolution reactions without an applied bias. While ultrahigh vacuum surface science techniques have provided useful insights, we still know relatively little about the structure of these electrodes in contact with electrolytes under operating conditions. Here, we report the surface structure evolution of a n-SrTiO3 electrode during water splitting, before and after "training" with an applied positive bias. Operando high-energy X-ray reflectivity measurements demonstrate that training the electrode irreversibly reorders the surface. Scanning electrochemical microscopy at open circuit correlates this training with a 3-fold increase of the activity toward the photo-induced water splitting. A novel first-principles joint density functional theory simulation, constrained to the X-ray data via a generalized penalty function, identifies an anatase-like structure as the more active, trained surface.

Exploiting dimensionality and defect mitigation to create tunable microwave dielectrics.

The miniaturization and integration of frequency-agile microwave circuits--relevant to electronically tunable filters, antennas, resonators and phase shifters--with microelectronics offers tantalizing device possibilities, yet requires thin films whose dielectric constant at gigahertz frequencies can be tuned by applying a quasi-static electric field. Appropriate systems such as BaxSr1-xTiO3 have a paraelectric-ferroelectric transition just below ambient temperature, providing high tunability. Unfortunately, such films suffer significant losses arising from defects. Recognizing that progress is stymied by dielectric loss, we start with a system with exceptionally low loss--Srn+1TinO3n+1 phases--in which (SrO)2 crystallographic shear planes provide an alternative to the formation of point defects for accommodating non-stoichiometry. Here we report the experimental realization of a highly tunable ground state arising from the emergence of a local ferroelectric instability in biaxially strained Srn+1TinO3n+1 phases with n ≥ 3 at frequencies up to 125 GHz. In contrast to traditional methods of modifying ferroelectrics-doping or strain-in this unique system an increase in the separation between the (SrO)2 planes, which can be achieved by changing n, bolsters the local ferroelectric instability. This new control parameter, n, can be exploited to achieve a figure of merit at room temperature that rivals all known tunable microwave dielectrics.