Dominique Appadoo

The Anodic Behavior of Planar and Porous Zinc Electrodes in Alkaline Electrolyte

The electrochemical performance of planar and porous zinc electrodes in an actual Zn/ MnO 2 battery using lithium hydroxide (LiOH) electrolyte has been investigated. A large discharge capacity of 220 mAh/g is delivered by porous zinc electrodes while planar electrodes only deliver 130 mAh/g. The porous anode improves the rate capability of the rechargeable alkaline battery while enhancing the utilization of the active material. Using scanning electron microscopy and IR spectroscopy, the surface morphology and composition of the Zn anodes were studied at the end of the discharge process. While zincate ions and ZnO products were found after the discharge at the surface of the planar anode, no evidence for these products was found in the porous anode. The porosity of this surface prevents the detrimental buildup of zincate ions at the anodic surface that leads to passivation.

Water ice nanoparticles: size and temperature effects on the mid-infrared spectrum

Mid-infrared spectra have been measured for cubic ice (I(c)) nanoparticles (3-150 nm diameter) formed by rapid collisional cooling over a wide range of temperatures (5-209 K). Spectral diagnostics, such as the ratio of surface related dangling OH to interior H-bonded OH stretch bands, reveal the manner in which particle size depends on bath gas temperature and density, and on water molecule concentration. For particles smaller than 5 nm strained intermolecular bonds on the surface and subsurface cause the predominant OH stretch peak position to be dramatically blue shifted by up to 40 cm(-1). In the size regime of 8-200 nm the position of the OH stretch absorption band maximum is relatively unaffected by particle size and it is possible to measure the temperature dependence of the peak location without influences from the surface or scattering. The band maximum shifts in a linear fashion from 3218 cm(-1) at 30 K to 3253 cm(-1) at 209 K, which may assist with temperature profiling of ice particles in atmospheric clouds and extraterrestrial systems. Over the same temperature range the librational mode band shifts very little, from 870 to 860 cm(-1). In the water stretching and bending regions discrete spectral features associated with the surface or sub-surface layers have been detected in particles as large as 80 nm.

Synthesis and Characterization of Li(Co0.5Ni0.5)PO4 Cathode for Li-Ion Aqueous Battery Applications

Olivine-type lithium orthophosphate Li(Co0.5Ni0.5)PO4 was synthesized in a solid state reaction at 800 degrees C in air. Infra-red spectroscopy, x-ray and neutron powder diffraction were used to characterize the as-prepared compound and its electro-oxidized analogue. Rietveld analysis was used to illustrate that the synthesized compound is isostructural with LiNiPO4 and LiCoPO4 with lattice parameters larger than the former and smaller than the latter. The Rietveld-refined Ni:Co ratio was found to be 0.498(4):0.502(4) and no evidence for long-range Ni: Co ordering or mixed Li/Ni/Co cation sites was found. The electro-oxidised electrode showed a mixture of two phases i.e. parent Li(Co0.5Ni0.5)PO4 and lithium extracted Li1-x(Co0.5Ni0.5)PO4 suggesting a delithiation process in aqueous electrolytes. Reversible Li transfer between a Li(Co0.5Ni0.5)PO4 electrode and an aqueous LiOH electrolyte was demonstrated.

SIZE AND TEMPERATURE DEPENDENCE IN THE FAR-IR SPECTRA OF WATER ICE PARTICLES

Spectra of water-ice aerosol particles have been measured in the far-IR region using synchrotron radiation. The particles in the nanoscale size regime of 1-100 nm were formed by rapid collisional cooling at temperatures ranging from 4 to 190 K. The spectra show the characteristic bands centered near 44 μm (230 cm–1) and 62 μm (160 cm–1) associated with the intermolecular lattice modes of crystalline ice at all temperatures, in contrast to previous studies of thin films formed by vapor deposition where amorphous ice is generated below 140 K. The bands shift to higher wavenumber values as the temperature is reduced, consistent with the trend seen in earlier studies, but in our experiments the actual peak positions in the aerosol particle spectra are consistently higher by ca. 4 cm–1. This finding has implications for the potential use of these spectral features as a temperature probe. The particle sizes are small enough for their spectra to be free of scattering effects, and therefore provide a means to assess imaginary refractive index values obtained through Kramers-Kronig analyses of thin film spectra.

Overview of high-resolution infrared measurement and analysis for atmospheric monitoring of halocarbons.

The current state of the art in recording and analyzing rotationally resolved vibration-rotation bands of atmospheric pollutant halocarbon species is reviewed. It is shown that in order to obtain molecular constants of sufficient accuracy to simulate the vibration-rotation structure over the range of atmospheric temperatures, it is necessary to obtain spectra at a range of temperatures using static cooling cells, supersonic jet expansions, and collisional cooling devices; employ sophisticated pattern recognition and analysis software; assign and fit spectral perturbations; and use spectral simulation and digital spectral subtraction (SASSI) to further simplify spectral bands for analysis. To demonstrate the techniques, an analysis of the ν(5) band of CH(37)ClF(2) in natural abundance is presented.

Structural characteristics of olivine Li(Mg0.5Ni0.5)PO4 via TEM analysis

The structural characteristics of olivine-type lithium orthophosphate Li(Mg0.5Ni0.5)PO4 synthesized via solid-state reaction have been studied using X-ray diffraction, ion beam technique, scanning electron microscopy, infrared spectroscopy, transmission electron microscopy and energy dispersive X-ray analysis. The parent LiNiPO4 compound can be synthesized in olivine structure without any evidence of secondary phases as impurities. The structural quality of the parent LiNiPO4 in the absence of secondary component phases resulted in the formation of hexagonal closed packed structure. The olivine analogue compound containing mixed M (M = Mg, Ni) cations, Li(Mg0.5Ni0.5)PO4 contained Li3PO4 as a second phase upon synthesis, however a carbothermal reduction method produced a single-phase compound. The redox behaviour of carbon-coated Li(Mg0.5Ni0.5)PO4 cathode in aqueous lithium hydroxide as the electrolyte showed reversible lithium intercalation.

Far-infrared absorption spectra of synthetically-prepared, ligated metal clusters with Au6, Au8, Au9 and Au6Pd metal cores

The far infra-red absorption spectra of a series of chemically synthesised, atomically precise phosphine-stabilised gold cluster compounds have been recorded using synchrotron light for the first time. Far-IR spectra of the Au6(Ph2P(CH2)3PPh2)4(NO3)2, Au8(PPh3)8(NO3)2, Au9(PPh3)8(NO3)3, and Pd(PPh3)Au6(PPh3)6(NO3)2 clusters reveal a complex series of peaks between 80 and 475 cm−1, for which all significant peaks can be unambiguously assigned by comparison with Density Functional Theory (DFT) geometry optimisations and frequency calculation. Strong absorptions in all spectra near 420 cm−1 are assigned to the P–Ph3 stretching vibrations. Distinct peaks within the spectrum of each specific cluster are assigned to the cluster core vibrations: 80.4 and 84.1 cm−1 (Au6) 165.1 and 166.4 cm−1 (Au8), 170.1 and 185.2 cm−1 (Au9), and 158.9, 195.2, and 206.7 cm−1 (Au6Pd). The positions of these peaks are similar to those observed to occur for the neutral Au7 cluster in the gas phase (Science, 2008, 321, 674–676). Au–P stretching vibrations only occur for Au6 near 420 cm−1, although they appear near 180 cm−1 for Au6Pd and involve gold core vibrations.

The Far-infrared Rotational Spectrum of Ethylene Oxide

High-resolution FTIR spectra of ethylene oxide have been measured in the far-infrared region using synchrotron radiation. A total of 1182 lines between 15 and 73?cm?1 were assigned, with J max?= 64, expanding upon previous studies that had recorded spectra up to 12?cm?1, J max?= 49. All available data were co-fitted to provide greatly imp- roved rotational constants for the ground vibrational state that are capable of predicting transitions up to 73?cm?1.

High-resolution Fourier-transform infrared spectroscopy of the ν6 and Coriolis perturbation allowed ν10 modes of ketenimine

High-resolution FTIR spectra of the short lived species ketenimine have been recorded in the region 700-1300 cm(-1) and over 1500 transitions of the ν(10) and ν(6) modes have been assigned. Effective rotational and centrifugal distortion parameters for the v(10) = 1 and v(6) = 1 (excluding K(a) = 5) states were determined by co-fitting transitions, and treating strong a- and c-axis Coriolis interactions between them. Other perturbations attributed to interactions with the v(8) = 2 and v(12) = 1 + v(8) = 1 dark-states were also observed and treated. The ν(10) transitions are predicted to be inherently very weak, but are enhanced by an intensity stealing effect with the highly IR active ν(6) mode. A mechanism for this intensity stealing in ketenimine is also detailed.

High-resolution Fourier-transform infrared spectroscopy of the Coriolis coupled ground state and ν7 mode of ketenimine

High resolution FTIR spectra of the short lived species ketenimine have been recorded in the regions 390-1300 cm(-1) and 20-110 cm(-1) using synchrotron radiation. Two thousand six hundred sixty transitions of the ν(7) band centered at 693 cm(-1) and 126 far-IR rotational transitions have been assigned. Rotational and centrifugal distortion parameters for the ν(7) mode were determined and local Fermi and b-axis Coriolis interactions with 2ν(12) are treated. A further refinement of the ground state, ν(12) and ν(8) parameters was also achieved, including the treatment of previously unrecognized ac-axis and ab-axis second order perturbations to the ground state.