Search Results (3)

Little is known about the temperature dependence of electron transfer occurring at real metal surfaces. For iron surfaces scratched in seven environments, we report Arrhenius activation energies obtained from the data of photoelectron emission (PE) and X-ray photoelectron spectroscopy (XPS). The environments were air, benzene, cyclohexane, water, methanol, ethanol, and acetone. PE was measured using a modified Geiger counter during repeated temperature scans in the 25–339 °C range under 210-nm-wavelength light irradiation and during light wavelength scans in the range 300 to 200 nm at 25, 200, and 339 °C. The standard XPS measurement of Fe 2p, Fe 3p, O 1s, and C 1s spectra was conducted after wavelength scan. The total number of electrons counted in the XPS measurement of the core spectra, which was called XPS intensity, strongly depended on the environments. The PE quantum yields during the temperature scan increased with temperature, and its activation energies (ΔE_aUp1) strongly depended on the environment, being in the range of 0.212 to 0.035 eV. The electron photoemission probability (αA) obtained from the PE during the wavelength scan increased with temperature, and its activation energies (ΔE_αA) were almost independent of the environments, being in the range of 0.113–0.074 eV. The environment dependence of the PE behavior obtained from temperature and wavelength scans was closely related to that of the XPS characteristics, in particular, the XPS intensities of O 1s and the O²⁻ component of the O 1s spectrum, the acid–base interaction between the environment molecule and Fe–OH, and the growth of non-stoichiometric Fe_xO. Furthermore, the origin of the αA was attributed to the escape depth of hot electrons across the overlayer. Full article

Herein, the post-mortem study on 16 Ah graphite//LiFePO₄ pouch cells is reported. Aiming to understand their failure mechanism, taking place when cycling at low temperature, the analysis of the cell components taken from different portions of the stacks and from different positions in the electrodes, is performed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoemission spectroscopy (XPS). Also, the recovered electrodes are used to reassemble half-cells for further cycle tests. The combination of the several techniques detects an inhomogeneous ageing of the electrodes along the stack and from the center to the edge of the electrode, most probably due to differences in the pressure experienced by the electrodes. Interestingly, XPS reveals that more electrolyte decomposition took place at the edge of the electrodes and at the outer part of the cell stack independently of the ageing conditions. Finally, the use of high cycling currents buffers the low temperature detrimental effects, resulting in longer cycle life and less inhomogeneities. Full article

High-resolution photoemission spectroscopy (HRPES) measurements were collected and density functional theory (DFT) calculations were performed to track the exposure-dependent variation of the adsorption structure of 2-thiophenecarboxaldehyde (C₄H₃SCHO: TPCA) on the Ge(100) 2 × 1 reconstructed surface at room temperature. In an effort to identify the most probable adsorption structures on the Ge(100)-2 × 1 reconstructed surface, we deposited TPCA molecules at low exposure and at high exposure and compared the differences between the electronic features measured using HRPES. The HRPES data suggested three possible adsorption structures of TPCA on the Ge(100)-2 × 1 reconstructed surface, and DFT calculations were used to determine the plausibility of these structures. HRPES analysis corroborated by DFT calculations, indicated that an S-dative bonded structure is the most probable adsorption structure at relatively low exposure levels, the [4 + 2] cycloadduct structure is the second most probable structure, and the [2 + 2]-C=O cycloadduct structure is the least probable structure on the Ge(100)-2 × 1 reconstructed surface at relatively high exposure levels. Full article