Dissociative adsorption of H2O on LiCoO2 (00l) surfaces: Co reduction induced by electron transfer from intrinsic defects.

Understanding the mechanism of the interaction of lithium ion conductors with water is crucial for both fundamental and technological points of view. Despite the generally accepted fact that water is one of main sources of the degradation of Li-ion recharge batteries, the physicochemical processes occurring at the water-lithium ion conductor interface are not fully understood. By using synchrotron X-ray photoelectron spectroscopy (SXPS) and O K- and Co L- X-ray absorption near edge structure (XANES), we evidence that H2O is dissociatively adsorbed on LiCoO2 thin film at room temperature resulting in the formation of OH groups and the accumulation of the negative charge at the surface accompanied by electron transfer to the initial empty Co3d (eg (*)) state. By considering the experimentally obtained energy diagram of the ionic conductor and water, direct charge transfer is not favorable due to a high difference in the chemical potential of the ionic conductor and electronic levels of the molecule. Here, we develop the model for the dissociative water adsorption which explains the electron transfer to LiCoO2 by using the atomistic approach. The model takes into account the intrinsic defects found on the surface (<2 nm depth) by using the depth resolved photoemission experiments and can be explored to other layered transition metal oxides to interpret the interaction of water with the surface of ionic conductors.

Extension of the Dubinin-Astakhov equation for evaluating the micropore size distribution of a modified carbon molecular sieve.

A new method for the characterization of the pore size distribution of microporous solids is applied on data obtained for activated carbon molecular sieve samples. In this method, based on the Dubinin-Astakhov equation, a simple numerical algorithm is used for the reconstruction of the micropore size distribution from the integral equation that represents the experimental nitrogen adsorption isotherm. The results are compared with the ones obtained on the basis of the well-known Horvath-Kawazoe method. The samples used in this study come from a carbon molecular sieve that has been treated with solutions of concentrated HNO3 at various temperatures and with solutions of H2O2 of various concentrations.