Lucia Zuin

The discharge rate capability of rechargeable Li–O2 batteries

The O2electrode in Li–O2cells was shown to exhibit gravimetric energy densities (considering the total weight of oxygen electrode in the discharged state) four times that of LiCoO2 with comparable gravimetric power. The discharge rate capability of Au-catalyzed Vulcan carbon and pure Vulcan carbon (VC) as the O2electrode was studied in the range of 100 to 2000 mA gcarbon−1. The discharge voltage and capacity of the Li−O2 cells were shown to decrease with increasing rates. Unlike propylene carbonate based electrolytes, the rate capability of Li−O2 cells tested with 1,2-dimethoxyethane was found not to be limited by oxygen transport in the electrolyte. X-Ray diffraction (XRD) showed lithium peroxide as the discharge product and no evidence of Li2CO3 and LiOH was found. It is hypothesized that higher discharge voltages of cells with Au/C than VC at low rates could have originated from higher oxygen reduction activity of Au/C. At high rates, higher discharge voltages with Au/C than VC could be attributed to faster lithium transport in nonstoichiometric and defective lithium peroxide formed upon discharge, which is supported by XRD and X-ray absorption near edge structure O and Li K edge data.

Phosphorus L2,3‐edge XANES: overview of reference compounds

Synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy is becoming an increasingly used tool for the element speciation in complex samples. For phosphorus (P) almost all XANES measurements have been carried out at the K-edge. The small number of distinctive features at the P K-edge makes in some cases the identification of different P forms difficult or impossible. As indicated by a few previous studies, the P L(2,3)-edge spectra were richer in spectral features than those of the P K-edge. However, experimentally consistent spectra of a wide range of reference compounds have not been published so far. In this study a library of spectral features is presented for a number of mineral P, organic P and P-bearing minerals for fingerprinting identification. Furthermore, the effect of radiation damage is shown for three compounds and measures are proposed to reduce it. The spectra library provided lays a basis for the identification of individual P forms in samples of unknown composition for a variety of scientific areas.

Commissioning and performance of the variable line spacing plane grating monochromator beamline at the Canadian Light Source

The variable line spacing plane grating monochromator beamline at the Canadian Light Source (CLS) employs three grazing incidence variable line spacing gratings to cover a photon energy range of 5-250 eV. It uses a 185 mm period length planar permanent magnet insertion device as the photon source, sharing a straight section with another soft x-ray beamline at the CLS. The commissioning and performance of the beamline is reported. The high resolution photoabsorption spectra of Ar and PF(5) gases are reported. A resolving power of over 40,000 for photons in the low energy region and >10,000 for a wider energy range (8-200 eV) can be achieved. A photon flux of up to 2 x 10(12) photons/s per 100 mA with slit settings of 50 microm has been measured.

Phosphorus Speciation in Agro-Industrial Byproducts: Sequential Fractionation, Solution 31P NMR, and P K- and L2,3-Edge XANES Spectroscopy

Little is known about P species in agro-industrial byproducts from developing countries, which may be either pollutants or valuable soil amendments. The present study speciated P in dry (COD) and wet (COW) coffee, sisal (SIS), barley malt (BEB) and sugar cane processing (FIC) byproducts, and filter cakes of linseed (LIC) and niger seed (NIC)with sequential fractionation, solution (31)P nuclear magnetic resonance (NMR) spectroscopy, and P K- and L(2,3)-edge X-ray absorption near-edge structure (XANES) spectroscopy. The sequential P fractionation recovered 59% to almost 100% of total P (P(t)), and more than 50% of P(t) was extracted by H(2)O and NaHCO(3) in five out of seven samples. Similarly, the NaOH + EDTA extraction for solution (31)P NMR recovered 48-94% of P(t). The (31)P NMR spectra revealed orthophosphate (6-81%), pyrophosphate (0-10%), and orthophosphate monoesters (6-94%). Orthophosphate predominated in COD, COW, SIS, and FIC, whereas BEB, UC, and NIC were rich in orthophosphate monoesters. The concentrations of P(i), and P(o) determined in the sequential and NaOH + EDTA extractions and (31)P NMR spectra were strongly and positively correlated (r = 0.88-1.00). Furthermore, the P K- and L(2,3)-edge XANES confirmed the H(2)SO(4)--P(i) detected in the sequential fractionation by unequivocal identification of Ca--P phases in a few samples. The results indicate that the combined use of all four analytical methods is crucial for comprehensive P speciation in environmental samples and the application of these byproducts to soil.

VLS‐PGM Beamline at the Canadian Light Source

The Variable Line Spacing Plane Grating Monochromator (VLS‐PGM) beamline is one of the several soft X‐ray beamlines at the Canadian Light Source (CLS). It is designed to produce photons ranging from 5.2 to 250 eV with a resolving power of 10,000. It uses a 185 mm period length Planar Permanent Magnet (PPM) insertion device as the photon source, sharing a straight with a 45 mm PPM undulator for the Spherical Grating Monochromator (SGM) beamline. The technical and optical performances of the beamline are discussed. Gas phase results obtained during the beamline commissioning demonstrated a resolving power of over 10,000 for all three gratings.

The Origin and Dynamics of Soft X-Ray-Excited Optical Luminescence of ZnO

The distinct optical emission from ZnO materials, nanoneedles and microcrystallites synthesized with different sizes and morphologies by a flow deposition technique, is investigated with X-ray excited optical luminescence (XEOL) and time-resolved X-ray excited optical luminescence (TR-XEOL) from a synchrotron light source at the O K and Zn L(3,2) edges. The innovative use of XEOL, allowing site-specific chemical information and luminescence information at the same time, is fundamental to provide direct evidence for the different behaviour and the crucial role of bulk and surface defects in the origin of ZnO optical emission, including dynamics. XEOL from highly crystalline ZnO nanoneedles is characterized by a sharp band-gap emission (~380 nm) and a broad red luminescence (~680 nm) related to surface defects. Luminescence from ZnO microcrystallites is mostly dominated by green emission (~510 nm) associated with defects in the core. TR-XEOL experiments show considerably faster decay dynamics in nanoneedles compared to microcrystallites for both band-gap emission and visible luminescence. Herein we make a fundamental step forward correlating for the first time the interplay of size, crystallinity, morphology and excitation energy with luminescence from ZnO materials.

Magnetism in lithium-oxygen discharge product

Nonaqueous lithium-oxygen batteries have a much superior theoretical gravimetric energy density compared to conventional lithium-ion batteries, and thus could render long-range electric vehicles a reality. A molecular-level understanding of the reversible formation of lithium peroxide in these batteries, the properties of major/minor discharge products, and the stability of the nonaqueous electrolytes is required to achieve successful lithium-oxygen batteries. We demonstrate that the major discharge product formed in the lithium-oxygen cell, lithium peroxide, exhibits a magnetic moment. These results are based on dc-magnetization measurements and a lithium-oxygen cell containing an ether-based electrolyte. The results are unexpected because bulk lithium peroxide has a significant band gap. Density functional calculations predict that superoxide-type surface oxygen groups with unpaired electrons exist on stoichiometric lithium peroxide crystalline surfaces and on nanoparticle surfaces; these computational results are consistent with the magnetic measurement of the discharged lithium peroxide product as well as EPR measurements on commercial lithium peroxide. The presence of superoxide-type surface oxygen groups with spin can play a role in the reversible formation and decomposition of lithium peroxide as well as the reversible formation and decomposition of electrolyte molecules.

Electronic structure of nanopolycrystalline pulsed laser deposited LaB6 films and single crystals: The boron perspective

We report an investigation of the electronic structure of LaB6 nanopolycrystalline pulsed laser deposited (PLD) film and single crystal with x-ray absorption near edge structures (XANES) spectroscopy at the B K-edge. The experimental results are compared with theoretical calculations using density functional theory, and real space multiple scattering. It is found that (i) the LaB6 PLD film is of high quality and metallic albeit it is a polycrystalline phase of nanocrystallites and (ii) the B K-edge XANES for the single crystal specimens exhibit well defined spectral features corresponding to the theoretical partial densities of states of B p character and the threshold energy is relatively low and free electronlike, revealing its metallic character. The implications of these observations to the enhancement in electron emission from the PLD films are discussed.

Chemical bonding in amorphous Si-coated carbon nanotubes as anodes for Li ion batteries: a XANES study

The nature of the chemical bonding in an amorphous Si-coated carbon nanotube (Si-CNT) anode, and its evolution upon electrochemical cycling, have been investigated using comprehensive X-ray absorption spectroscopy (XANES) at the Si L- and K-edges, along with the C and O K-edges. The Si nanolayer on the CNT is found to be anchored to the CNT via Si–O–C bonding. This bond weakens upon electrochemical cycling, accompanied by the generation of Li2CO3 on the surface of the Si-CNT. These findings are crucial in designing further improved Si–C composite anodes for lithium ion batteries.

The crystallization of MgO–Al2O3–SiO2–ZrO2 glass-ceramics with and without the addition of Y2O3 – a combined STEM/XANES study

Glasses with the mol% composition of 51.9SiO2/21.2Al2O3/21.2MgO/5.7ZrO2 without and with the addition of 2.5 mol% Y2O3 were melted and subsequently transformed into glass-ceramics via annealing. Both glass-ceramics show strong differences in the microstructure and in the phase composition after crystallization at 950 °C for 5 h and subsequently at 1060 °C for different annealing times. In the glass without Y2O3, the main crystal phase is a quartz solid solution accompanied by the precipitation of ZrO2 and spinel. By contrast, glass-ceramics without the presence of a quartz solid solution were observed after the crystallization of the Y2O3-containing glass, using the same heat treatment. This is confirmed by analytical scanning transmission electron microscopy analysis and X-ray absorption near-edge structure spectroscopy data gathered at the Zr L2-, Y L2,3-, Si K- and Al L-edges. Furthermore, using X-ray absorption spectroscopy the coordination of the respective elements is analysed, and changes of the coordination during crystallization are monitored.