Surface Structural Disordering in Graphite upon Lithium Intercalation/Deintercalation

We report on the origin of the surface structural disordering in graphite anodes induced by lithium intercalation and deintercalation processes. Average Raman spectra of graphitic anodes reveal that cycling at potentials that correspond to low lithium concentrations in LixC (0 \leq x < 0.16) is responsible for most of the structural damage observed at the graphite surface. The extent of surface structural disorder in graphite is significantly reduced for the anodes that were cycled at potentials where stage-1 and stage-2 compounds (x > 0.33) are present. Electrochemical impedance spectra show larger interfacial impedance for the electrodes that were fully delithiated during cycling as compared to electrodes that were cycled at lower potentials (U < 0.15 V vs. Li/Li+). Steep Li+ surface-bulk concentration gradients at the surface of graphite during early stages of intercalation processes, and the inherent increase of the LixC d-spacing tend to induce local stresses at the edges of graphene layers, and lead to the breakage of C-C bonds. The exposed graphite edge sites react with the electrolyte to (re)form the SEI layer, which leads to gradual degradation of the graphite anode, and causes reversible capacity loss in a lithium-ion battery.Comment: 12 pages, 5 figure

Directing Selectivity of Electrochemical Carbon Dioxide Reduction Using Plasmonics

Catalysts for electrochemical carbon dioxide reduction in aqueous electrolytes suffer from high energy input requirements, competition with hydrogen evolution from water reduction, and low product selectivity. Theory suggests that plasmonic catalysts can be tuned to selectively lower the energy barrier for a specific reaction in a set of competitive reactions, but there has been little experimental evidence demonstrating plasmon-driven selectivity in complicated multielectron electrochemical processes. Here, the photoactivity at a plasmonically active silver thin film electrode at small cathodic potentials selectively generates carbon monoxide while simultaneously suppressing hydrogen production. At larger cathodic potentials, the photoactivity promotes production of methanol and formate. Methanol production is observed only under illumination, not in dark conditions. The preference of the plasmonic activity for carbon dioxide reduction over hydrogen evolution and the ability to tune plasmonic activity with voltage demonstrates that plasmonics provide a promising approach to promote complex electrochemical reactions over other competing reactions

Important Considerations in Plasmon-Enhanced Electrochemical Conversion at Voltage-Biased Electrodes.

In this perspective we compare plasmon-enhanced electrochemical conversion (PEEC) with photoelectrochemistry (PEC). PEEC is the oxidation or reduction of a reactant at the illuminated surface of a plasmonic metal (or other conductive material) while a potential bias is applied. PEC uses solar light to generate photoexcited electron-hole pairs to drive an electrochemical reaction at a biased or unbiased semiconductor photoelectrode. The mechanism of photoexcitation of charge carriers is different between PEEC and PEC. Here we explore how this difference affects the response of PEEC and PEC systems to changes in light, temperature, and surface morphology of the photoelectrode

In Situ ATR-SEIRAS of Carbon Dioxide Reduction at a Plasmonic Silver Cathode.

Illumination of a voltage-biased plasmonic Ag cathode during CO2 reduction results in a suppression of the H2 evolution reaction while enhancing CO2 reduction. This effect has been shown to be photonic rather than thermal, but the exact plasmonic mechanism is unknown. Here, we conduct an in situ ATR-SEIRAS (attenuated total reflectance-surface-enhanced infrared absorption spectroscopy) study of a sputtered thin film Ag cathode on a Ge ATR crystal in CO2-saturated 0.1 M KHCO3 over a range of potentials under both dark and illuminated (365 nm, 125 mW cm-2) conditions to elucidate the nature of this plasmonic enhancement. We find that the onset potential of CO2 reduction to adsorbed CO on the Ag surface is -0.25 VRHE and is identical in the light and the dark. As the production of gaseous CO is detected in the light near this onset potential but is not observed in the dark until -0.5 VRHE, we conclude that the light must be assisting the desorption of CO from the surface. Furthermore, the HCO3- wavenumber and peak area increase immediately upon illumination, precluding a thermal effect. We propose that the enhanced local electric field that results from the localized surface plasmon resonance (LSPR) is strengthening the HCO3- bond, further increasing the local pH. This would account for the decrease in H2 formation and increase the CO2 reduction products in the light

Consideration of Non-Structural Internal Debris in Siting of Blast Resistant Modules

PresentationBlast resistant modules (BRMs) have become prevalent at petroleum refining and chemical processing facilities over the last decade. A primary rationale for utilizing a BRM is to allow a building housing essential personnel (e.g., operators) to be sited near the process units for which they are responsible. BRMs are selected based on a pressure-rating and response level (typically Low, Medium, or High). A common misconception is that a BRM will be undamaged and reusable for a specified blast overpressure rating, and such buildings are often incorrectly referred to as “blast-proof”. In order to absorb blast energy, the walls and roof of a BRM are designed to undergo transient accelerations and displacements. The allowable displacements are dictated by the selected response level, and that stated response level does not directly communicate the hazard associated with wall deflection and non-structural debris. Displacement and acceleration of a BRM wall can lead to significant non-structural internal debris hazards, as has been observed in testing programs and incident investigations. These hazards become more severe as the BRM blast rating and response level increases. Such hazards are sometimes overlooked when siting a BRM. A structural analysis of a BRM may be required to predict wall accelerations in order to quantify these hazards and properly site the BRM, rather than relying solely on a blast overpressure rating. This paper provides insight into the hazards associated with interior finish-out and wall-mounted items commonly observed in BRMs, and the means necessary to mitigate these hazards

Modification des polymères conducteurs avec de petites particules métalliques; propriétés des films de polypyrrole et de polyaniline platines

The properties of two π-conjugated conducting polymers, polypyrrole, and polyaniline, modified with small amounts of Pt, have been investigated. Both polymers were prepared by electrochemical (cyclic voltammetric) polymerization in the form of thin films (less than 1 μm for polypyrrole, ca. 50-μm thick for polyaniline). It is shown that incorporation, via electrodeposition, of small amount of dispersed Pt particles, inside the polymer film, leads to radical change of its properties. Thus, the polypyrrole film electrode containing ca. 200 μg · cm-2 of Pt exhibits remarkably stable electrocatalytic activity towards anodic oxidation of an important fuel cell reactant – CH3OH. In contrast with the bulk Pt metal or the Pt dispersed on other supports, a polypyrrole/Pt composite does apparently not undergo poisoning, even in the course of prolonged oxidation runs. We show also that the incorporation of Pt microparticles, into several tens of μm thick polyniline films, results in a large enhancement of their redox switching rate between isolating and conducting states and vice versa

Microstructured optical fiber-based biosensors: reversible and nanoliter-scale measurement of zinc ions

Published: May 6, 2016Sensing platforms that allow rapid and efficient detection of metal ions would have applications in disease diagnosis and study, as well as environmental sensing. Here, we report the first microstructured optical fiber-based biosensor for the reversible and nanoliter-scale measurement of metal ions. Specifically, a photoswitchable spiropyran Zn(2+) sensor is incorporated within the microenvironment of a liposome attached to microstructured optical fibers (exposed-core and suspended-core microstructured optical fibers). Both fiber-based platforms retains high selectivity of ion binding associated with a small molecule sensor, while also allowing nanoliter volume sampling and on/off switching. We have demonstrated that multiple measurements can be made on a single sample without the need to change the sensor. The ability of the new sensing platform to sense Zn(2+) in pleural lavage and nasopharynx of mice was compared to that of established ion sensing methodologies such as inductively coupled plasma mass spectrometry (ICP-MS) and a commercially available fluorophore (Fluozin-3), where the optical-fiber-based sensor provides a significant advantage in that it allows the use of nanoliter (nL) sampling when compared to ICP-MS (mL) and FluoZin-3 (μL). This work paves the way to a generic approach for developing surface-based ion sensors using a range of sensor molecules, which can be attached to a surface without the need for its chemical modification and presents an opportunity for the development of new and highly specific ion sensors for real time sensing applications.Sabrina Heng, Christopher A. McDevitt, Roman Kostecki, Jacqueline R. Morey, Bart A. Eijkelkamp, Heike Ebendorff-Heidepriem, Tanya M. Monro, and Andrew D. Abel

Elucidating the Limit of Li Insertion into the Spinel Li4Ti5O12

In this work, we show that the well-known lithium-ion anode material, Li4Ti5O12, exhibits exceptionally high initial capacity of 310 mAh g-1 when it is discharged to 0.01 V. It maintains a reversible capacity of 230 mAh g-1, far exceeding the "theoretical" capacity of 175 mAh g-1 when this anode is lithiated to the composition Li7Ti5O12. Neutron diffraction analyses identify that additional Li reversibly enters into the Li7Ti5O12 to form Li8Ti5O12. density functional theory (DFT) calculations reveal the average potentials of the Li4Ti5O12 to Li7Ti5O12 step and the Li7Ti5O12 to Li8Ti5O12 step are 1.57 and 0.19 V, respectively, which are in excellent agreement with experimental results. Transmission electron microscopy (TEM) studies confirm that the irreversible capacity of Li4Ti5O12 during its first cycle originates from the formation of a solid electrolyte interface (SEI) layer. This work clarifies the fundamental lithiation mechanism of the Li4Ti5O12, when lithiated to 0.01 V vs Li