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Diffusion coefficients are important parameters for the characterization of new electrode materials, but they are also essential for the study of cell aging and as input parameters in battery modeling. In this report, the applicability of the galvanostatic intermittent titration technique (GITT) on commercial cells is studied. A GITT protocol is applied on a set of commercial cells with graphite anodes and various cathode materials. The cell response is then compared with the ones of the individual electrodes, obtained in three-electrode and half-cell configurations. In particular, mostly due to the particular potential profile of graphite, the full cell GITT response corresponds to the anode and cathode response at low and high state of charge, respectively. Therefore, it is possible to estimate the diffusion coefficients of the individual electrodes by a simple experiment on commercial cells, although only in limited ranges of SOC. If the experiments are performed at different temperatures, it is also possible to determine the activation energies of the diffusion coefficients. In conclusion, GITT allows an estimation of the diffusivity data in commercial cells, and can be therefore used as fast analytical tool for the study of aging and for the modeling of lithium-ion batteries.
The oxygen bearing gases of the atmosphere in a reheating furnace oxidise the feedstock producing scale on the surface of the metal and, for high carbon steels, cause decarburisation of the surface layers. Modelling of these effects has to take into account the competitive nature of the two processes, scale formation and decarburisation, and complications that arise from changes in the controlling mechanism. Initially, the rate of scale formation may be controlled by effects in the gas phase, or nucleation of scale on the metal surface. Subsequently, scale growth is influenced by the gas composition and may be disturbed by the accumulation of oxidation products at the scalemetal interface. Voids and cracks within the scale may either inhibit solid state diffusion within the scale or provide channels for oxidising gas to access the scale-metal interface. For decarburisation, complications arise if a ferrite rim creates a step in the carbon profile or if retention of carbon monoxide within the scale provides a thermodynamic barrier to the reaction. This paper considers these complications and how they may be handled in mathematical models.
Thin film sandwich samples have been prepared of copper phthalocyanine ultrathin solid films with incorporated metal (silver, indium) nanoclusters, surrounded by an amorphous silicon environment. The samples were investigated by transmission electron microscopy in both lateral and cross-sectional geometries. In view of the optical properties, we observed a gradual blue wavelength shift of the localized metal cluster plasmon excitation for about 300 nm accompanying an equivalent copper phthalocyanine thickness increase from 'zero' to a threshold thickness of about 4 nm. We attribute this behaviour to the formation of bulk-like optical properties of the copper phthalocyanine film, which is completed at the observed equivalent threshold thickness.
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