Lithium deintercalation of Li x CoO 2 from x ) 1 to x ≈ 0 has been carried out electrochemically. The changes in the electronic structure from LiCoO 2 to CoO 2 have been investigated by X-ray photoelectron spectroscopy (XPS) to bring some new developments about the electron transfer mechanisms upon lithium deintercalation. All available XPS core peaks (Co 2p, Co 3p, Co 3s, O 1s, F 1s, P 2p, C 1s) and valence spectra have been analyzed. The contributions of the electrode material and of the electrode/electrolyte interface have been clearly distinguished. We show that cobalt and oxygen simultaneously undergo a partial oxidation process and that the sole participation of oxygen atoms to the charge transfer process, as it is sometimes assumed, can be excluded. The surface film consists of organic and inorganic species resulting from degradation of the electrolyte.
Advanced (1)H, (13)C, and (31)P solution- and solid-state NMR studies combined with XPS were used to probe, at the molecular scale, the composition (of the core, the shell, and the interface) and the surface chemistry of InP/ZnS core/shell quantum dots prepared via a non-coordinating solvent strategy. The interface between the mismatched InP and ZnS phases is composed of an amorphous mixed oxide phase incorporating InPO(x) (with x = 3 and predominantly 4), In(2)O(3), and InO(y)(OH)(3-2y) (y = 0, 1). Thanks to the analysis of the underlying reaction mechanisms, we demonstrate that the oxidation of the upper part of the InP core is the consequence of oxidative conditions brought by decarboxylative coupling reactions (ketonization). These reactions occur during both the core preparation and the coating process, but according to different mechanisms.
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