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Daniel Duarte-Ruiz

Publications and source records attributed to Daniel Duarte-Ruiz.

2 recordsLinked to original sources

Decoding Oxygen K-edge Fingerprints of NCM-811 Degradation via Ab Initio Many-Body Theory and High-Throughput Screening of Crystal Proxies

The degradation of LiNi$_{0.8}$Co$_{0.1}$Mn$_{0.1}$O$_2$ (NCM-811) in Li-ion batteries produces complex transition-metal oxides and binary phases that fundamentally limit cathode performance. While identifying these degradation products via X-ray absorption spectroscopy (XAS) is essential for mitigating electrochemical performance loss, interpretation remains challenging due to the structural complexity of real-world samples. In this work, we present an integrated theoretical-experimental framework combining high-resolution oxygen K-edge XAS with \textit{ab initio} simulations based on many-body perturbation theory and high-throughput screening from density functional theory. We first evaluate the spectroscopic fingerprints of eight layered, spinel, and nominal rock-salt reference oxides, identifying discrepancies between the idealized single-crystal bulk phase and experimental spectra. Using high-throughput screening to analyze the oxygen $p$-projected density of states of 38 distinct polymorphs of NiO, CoO, and MnO, we propose that the spectral differences can emerge, among other factors, from a structural ensemble of local variations represented here by simplified structural proxies. Our work establishes a viable and rigorous computational pathway to interpret the complex landscape of degraded battery materials.

cond-mat.mtrl-sci

Electronic Structure and Core Spectroscopy of Scandium Fluoride Polymorphs

The microscopic knowledge of the structural, energetic, and electronic properties of scandium fluoride is still incomplete, despite the relevance of this material as an intermediate for the manufacturing of Al-Sc alloys. In a work based on first-principles calculations and x-ray spectroscopy, we assess the stability and the electronic structure of six computationally predicted ScF$_3$ polymorphs, two of which correspond to experimentally resolved single-crystal phases. In the theoretical analysis based on density-functional theory (DFT), we identify similarities among the polymorphs based on their formation energies, charge-density distribution, and electronic properties (band gaps and density of states). We find striking analogies between the results obtained for the low- and high-temperature phases of the material, indirectly confirming that the transition occurring between them mainly consists of a rigid rotation of the lattice. With this knowledge, we examine the x-ray absorption spectra from the Sc and F K-edge contrasting first-principles results obtained from the solution of the Bethe-Salpeter equation on top of all-electron DFT with high-energy-resolution fluorescence detection measurements. The analysis of the computational results sheds light on the electronic origin of the absorption maxima and provides information on the prominent excitonic effects that characterize all spectra. Comparison with measurements confirms that the sample is mainly composed of the high- and low-temperature polymorphs of ScF$_3$. However, some fine details in the experimental results suggest that the probed powder sample may contain defects and/or residual traces of metastable polymorphs.

cond-mat.mtrl-sci