Ex situ X-­Ray absorption study of Li-­rich layered cathode material Li[Li0.2Mn0.56Ni0.16Co0.08]O2

The Li-rich layered transition metal oxides (LLOs) Li2MnO3-LiMO2 (M=Mn, Co, Ni, etc.) have drawn considerable attention as cathode materials for rechargeable lithium batteries. They generate large reversible capacities but the fundamental reaction mechanism and structural perturbations during cycling remain controversial. In the present thesis, ex situ X-ray absorption spectroscopy (XAS) measurements were performed on Li[Li0.2Mn0.56Ni0.16Co0.08]O2 at different stage of charge during electrochemical oxidation/reduction. K-edge spectra of Co, Mn and Ni were recorded through a voltage range of 3.7-4.8V vs. Li/Li+, which consist of X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS). Oxidation states during initial charge were discussed based on values from literature as well as XANES analysis. Information about bond distance, coordination number as well as corresponding Debye-Waller factor were extracted from Gnxas analysis of raw data in the EXAFS region. The possibility of oxygen participation in the initial charge was discussed. Co and Ni prove to take part in the oxidation/reduction process while Mn remain in the tetravalent state. The cathode material appears to retain good structural short-range order during charge-discharge. A resemblance of the pristine sample and sample 4 was discovered which was firstly reported for similar compounds.

Heavily obscured AGN: an ideal laboratory to study the early co-evolution of galaxies and black holes

Obscured AGN are a crucial ingredient to understand the full growth history of super massive black holes and the coevolution with their host galaxies, since they constitute the bulk of the BH accretion. In the distant Universe, many of them are hosted by submillimeter galaxies (SMGs), characterized by a high production of stars and a very fast consumption of gas. Therefore, the analysis of this class of objects is fundamental to investigate the role of the ISM in the early coevolution of galaxies and black holes. We present a multiwavelength study of a sample of six obscured X-ray selected AGN at z>2.5 in the CDF-S, detected in the far-IR/submm bands. We performed the X-ray spectral analysis based on the 7Ms Chandra dataset, which provides the best X-ray spectral information currently available for distant AGN. We were able to place constraints on the obscuring column densities and the intrinsic luminosities of our targets. Moreover, we built up the UV to FIR spectral energy distributions (SEDs) by combining the broad-band photometry from CANDELS and the Herschel catalogs, and analyzed them by means of an SED decomposition technique. Therefore, we derived important physical parameters of both the host galaxy and the AGN. In addition, we obtained, through an empirical calibration, the gas mass in the host galaxy and assessed the galaxy sizes in order to estimate the column density associated with the host ISM. The comparison of the ISM column densities with the values measured from the X-ray spectral analysis pointed out that the contribution of the host ISM to the obscuration of the AGN emission can be substantial, ranging from ~10% up to ~100% of the value derived from the X-ray spectra. The absorption may occur at different physical scales in these sources and, in particular, the medium in the host galaxy is an ingredient that should be taken into account, since it may have a relevant role in driving the early co-evolution of galaxies with their black holes.