arXiv subjects

Antonella Iadecola

Publications and source records attributed to Antonella Iadecola.

8 recordsLinked to original sources

arXiv2026

Spatially inhomogeneous delithiation in LiNiO2 positive electrode: the effect of X-rays dose

Operando synchrotron X-ray techniques have become essential tools for investigating rechargeable batteries as they provide real-time insights into electrochemical processes. However, the high brilliance of synchrotron radiation can alter the electrochemical mechanisms within the battery, thereby compromising the reliability and reproducibility of operando measurements. In this study, we introduce a novel methodology that directly correlates the local X-ray dose with the Ni4+/Ni3+ redox activity in a LiNiO2 positive electrode. Full-field transmission X-ray absorption spectroscopy imaging (FFI-XAS) is employed to probe the charge-compensation mechanism during lithium extraction at the micrometre scale, using two beam configurations with different focal distances (far-focus and near-focus). While the spatially averaged XAS spectra exhibit sluggish reaction, regions exposed to lower dose rates exhibit the expected electrochemical evolution. This contrast enables the identification of a dose threshold for reliable operando measurements. This approach establishes a practical dose limit and provides spatially resolved insight into beam-induced effects, offering both a diagnostic framework and a pathway toward more reliable operando experiments.

cond-mat.mtrl-sci↗

arXiv2026

A large scale multi-modal workflow for battery characterization: from concept to implementation

The development of material acceleration platforms in battery research requires integrating complementary techniques and correlating heterogeneous experimental datasets. Here, this challenge is tackled in a large-scale multimodal program involving fifteen laboratories and facilities across Europe. Coordinated multi-site experiments are performed on state-of-the-art graphite / LiNiO2 Li-ion full cells to address two archetypal scientific questions: is the electrolyte composition impacting electrode properties, and how do electrode materials evolve when cells are cycled to their end-of-life? A fully standardized and centralized workflow is demonstrated, from sample production and delivery, to metadata and data handling, generating seventy-five concatenated datasets shared among all partners. Their integrated analysis shows that scientific conclusions depend critically on both the observable chosen to describe electrode properties, and the measurement technique employed. Individual experiments provide detailed information into specific aspects, such as crystal structures, redox activity, surface processes, morphology, etc., but can also function as binary diagnostic tool. Two-dimensional observable-technique patterns are introduced, in which each pixel encodes a yes, no or uncertain answer to a given scientific question. These patterns serve as multi-property metaviews, e.g. visual genotypes, enabling to classify material behavior and technique suitability according to predefined user demand and criteria, highlighting the interdependencies between measurement choices, extracted parameters and scientific interpretation. This multimodal workflow establishes a proof-of-concept for correlative analysis and underscores challenges toward fully integrated, automated and holistic approaches in energy material science.

physics.app-ph↗

arXiv2025

Insights on the role of the covalent Ni-O bonds in LiNiO2 positive electrodes: A combined hard X-ray spectroscopy study

The interest in Ni-rich layered oxide positive electrode materials has been increasing due to its wide applicability particularly in electric vehicles as high capacity and high energy density electrode materials. However, the Ni-O bond array which builds the overall framework and plays a critical role in the charge compensation mechanism of the material requires deeper understanding. This work presents a correlative approach elucidating the role of the local highly covalent Ni-O bonds in LiNiO2 (LNO) model material. Pristine and electrochemically obtained LNO positive electrodes are analyzed using ex situ X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) to compare the average and local structural evolution upon Li+ ion de-intercalation. Insights from Ni K-edge X-ray absorption near-edge structure (XANES) and non-resonant Ni Kbeta X-ray emission spectroscopy (XES) spectra are combined to track the electronic environment of Ni. X-ray Raman scattering (XRS) spectra at the Ni L2,3-edges and O K-edge provide direct bulk electronic information with regards to the interplay between Ni 3d and O 2p states. The overall findings imply that O plays a significant role in the charge compensation process, contributing to the substantial negative charge transfer from the O 2p orbitals, because of the covalency in the Ni-O bonds inside the NiO2 framework within the edge-sharing NiO6 octahedra. The utilization of complementary X-ray spectroscopy techniques clarifies the intricate electronic environment of LNO, which is helpful in understanding Ni-rich positive electrode materials and offering new insights into their covalent nature.

cond-mat.mtrl-sci↗

arXiv2024

A fundamental correlative spectroscopic study on LixNiO2 and NaNiO2

The intimate correlation between the local atomic arrangement and electronic states in Li-ion battery cathode materials plays a crucial role in determining their electrochemical properties, including capacity, cycling stability, and rate capability. Despite almost 30 years of research efforts on high performance cathodes based on Ni rich layered oxides, there is still no consensus on LiNiO2 local atomic and electronic structure. Ni sites could be either Jahn-Teller distorted or bond disproportionated and the role of Ni and oxygen in the charge compensation mechanism remains unclear. In this study, we compare the local and electronic structure of LiNiO2 and NaNiO2, a long-range Jahn-Teller system, using a novel approach which aims at correlating the results from bulk spectroscopy techniques, particularly under operando conditions, obtained on standard samples to ensure sample interoperability and enhance the reliability and robustness of our results. Despite being a site-selective and local technique, XAS is unable to discriminate between the proposed scenarios, as confirmed also by theoretical calculations. On the contrary, Raman spectroscopy show local structural differences between monoclinic distorted NaNiO2 and rhombohedral LiNiO2. Additionally, HAXPES confirms the presence of multiple formal oxidation states for Ni, and RIXS data provides evidence of 3d8 states, confirming the negative charge transfer character of Ni and some degree of bond disproportionation in LiNiO2. Regarding the charge compensation mechanism, XRS and RIXS support the participation of oxygen holes in the redox activity, while Raman spectroscopy does not detect molecular oxygen. By combing several high-fidelity spectroscopy datasets, this study shows the value of correlative characterization workflows to provide insights into complex structural-electrochemical relationships.

cond-mat.mtrl-sci↗

arXiv2016

Efficient artificial mineralization route to decontaminate Arsenic(III) polluted water -the Tooeleite Way

Increasing exposure to arsenic (As) contaminated ground water is a great threat to humanity. Suitable technology for As immobilization and removal from water, especially for As(III) than As(V), is not available yet. However, it is known that As(III) is more toxic than As(V) and most groundwater aquifers, particularly the Gangetic basin in India, is alarmingly contaminated with it. In search of a viable solution here, we took a cue from the natural mineralization of Tooeleite, a mineral containing Fe(III) and As(III)ions, grown under acidic condition, in presence of SO42- ions. Complying to this natural process, we could grow and separate Tooeleite-like templates from Fe(III) and As(III) containing water at overall circumneutral pH and in absence of SO42- ions by using highly polar Zn-only ends of wurtzite ZnS nanorods as insoluble nano-acidic-surfaces. The central idea here is to exploit these insoluble nano-acidic-surfaces (called as INAS in the manuscript) as nucleation centres for Tooeleite growth while keeping the overall pH of the aqueous media neutral. Therefore, we propose a novel method of artificial mineralization of As(III) by mimicking a natural process at nanoscale.

cond-mat.mtrl-sci↗

arXiv2013

Temperature dependent local atomic displacements in Ru substituted SmFe_{1-x}Ru_{x}AsO_{0.85}F_{0.15} superconductors

Local structure of SmFe$_{1-x}$Ru$_x$AsO$_{0.85}$F$_{0.15}$ ($x$ = 0.0, 0.05, 0.25 and 0.5) superconductors has been investigated by temperature dependent As $K$-edge extended x-ray absorption fine structure. The effect of Ru substitution remains confined to the iron-arsenide layer but neither the static disorder nor the Fe-As bond strength suffers any change for $x \le$ 0.25. With further Ru substitution the static disorder increases while the Fe-As bond strength remains unchanged. Also, the Ru-As distance ($\sim$2.42 Å), different from the Fe-As distance ($\sim$2.39 Å), does not show any change in its force constant with the Ru substitution. These observations suggest that the SmFe$_{1-x}$Ru$_x$AsO$_{0.85}$F$_{0.15}$ system breaks down to coexisting local electronic phases on isoelectric substitution in the active FeAs layer.

cond-mat.supr-con↗

arXiv2012

Large local disorder in the superconducting K_{0.8}Fe_{1.6}Se_{2} studied by extended x-ray absorption fine structure

We have measured local structure of superconducting K_{0.8}Fe_{1.6}Se_{2} chalcogenide (T_{c}=31.8 K) by temperature dependent polarized extended x-ray absorption fine structure (EXAFS) at the Fe and Se K-edges. We find that the system is characterized by a large local disorder. The Fe-Se and Fe-Fe distances are found to be shorter than the distances measured by diffraction, while the corresponding mean square relative displacements reveal large Fe-site disorder and relatively large c-axis disorder. The local force constant for Fe-Se bondlength (k ~ 5.8 eV/Å^{2}) is similar to the one found in the binary FeSe superconductor, however, the Fe-Fe bondlength appears to get flexible (k ~ 2.1 eV/Å^{2}) in comparison to the binary FeSe (k ~ 3.5 eV/Å^{2}), an indication of partly relaxed Fe-Fe networks in K_{0.8}Fe_{1.6}Se_{2}. The results suggest glassy nature of the title system, with the superconductivity being similar to the one in the granular materials.

cond-mat.supr-con↗

arXiv2011

Temperature dependent local structure of NdFeAsO1-xFx system using arsenic K-edge extended x-ray absorption fine structure

Local structure of NdFeAsO$_{1-x}$F$_{x}$ ($x$=0.0, 0.05, 0.15 and 0.18) high temperature iron pnictide superconductor system is studied using arsenic $K$-edge extended x-ray absorption fine structure measurements as a function of temperature. Fe-As bondlength shows only a weak temperature and F-substitution dependence, consistent with the strong covalent nature of this bond. The temperature dependence of the mean-square relative-displacements of the Fe-As bondlength are well described by the correlated-Einstein model for all the samples, but with different Einstein-temperatures for the superconducting and non-superconducting samples. The results indicate distinct local Fe-As lattice dynamics in the superconducting and non-superconducting iron-pnictide systems.

cond-mat.supr-con↗