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226 results on '"Iadecola, Antonella"'

1. A fundamental correlative spectroscopic study on LixNiO2 and NaNiO2

Author

Jacquet, Quentin, Mozhzhukhina, Nataliia, Gillespie, Peter N. O., Wittmann, Gilles, Ramirez, Lucia Perez, Capone, Federico G., Rueff, Jean-Pascal, Belin, Stephanie, Dedryvère, Rémi, Stievano, Lorenzo, Matic, Aleksandar, Suard, Emmanuelle, Brookes, Nicholas B., Longo, Alessandro, Prezzi, Deborah, Lyonnard, Sandrine, and Iadecola, Antonella

Subjects
Condensed Matter - Materials Science
Abstract

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.

Published
2024
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8. A Fundamental Correlative Spectroscopic Study on Li1‐xNiO2 and NaNiO2.

Author

Jacquet, Quentin, Mozhzhukhina, Nataliia, Gillespie, Peter N.O., Wittmann, Gilles, Ramirez, Lucia Perez, Capone, Federico G., Rueff, Jean‐Pascal, Belin, Stephanie, Dedryvère, Rémi, Stievano, Lorenzo, Matic, Aleksandar, Suard, Emmanuelle, Brookes, Nicholas B., Longo, Alessandro, Prezzi, Deborah, Lyonnard, Sandrine, and Iadecola, Antonella

Abstract

The intricate relationship between local atomic arrangements and electronic states significantly influences the electrochemical properties of Li‐ion battery cathode materials. Despite decades of investigation, a consensus regarding the local atomic and electronic structure of LiNiO2 remains elusive. This ambiguity stems from the potential distortion of Ni sites, either via Jahn‐Teller (JT) distortion or bond disproportionation (BD), complicating the understanding of the charge compensation mechanism involving Ni and O. This study compares the structures of LiNiO2 and NaNiO2, a JT system, using an innovative approach that integrates bulk spectroscopy techniques on standardized interoperable samples for enhanced reliability. While X‐ray absorption spectroscopy and theoretical calculations fail to differentiate between the proposed scenarios, Raman spectroscopy highlights local structural distinctions between monoclinic NaNiO2 and rhombohedral LiNiO2. HAXPES confirms various formal oxidation states for Ni, supported by RIXS data indicating 3d8 states, emphasizing negative charge transfer from Ni and some bond disproportionation in LiNiO2. Regarding charge compensation, XRS and RIXS suggest oxygen hole involvement in redox activity, whereas Raman spectroscopy does not detect molecular oxygen. This comprehensive spectroscopic analysis highlights the importance of correlative characterization workflows in elucidating complex structural‐electrochemical relationships. [ABSTRACT FROM AUTHOR]

Published
2024
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9. Zn Distribution and Chemical Speciation in Marine Biominerals: An Example on Bivalve and Foraminifera Shells from Polluted Sites

Author

De Giudici, Giovanni, Meneghini, Carlo, Buosi, Carla, Carlomagno, Ilaria, Aquilanti, Giuliana, Araki, Tohru, Bedolla, Diana E., Casu, Maria Antonietta, Cherchi, Antonietta, Gianoncelli, Alessandra, Iadecola, Antonella, Kuncser, Andrei C., Maraloiu, V. Adrian, Mathon, Olivier, Rimondi, Valentina, Zuddas, Pierpaolo, Medas, Daniela, Di Cicco, Andrea, editor, Giuli, Gabriele, editor, and Trapananti, Angela, editor

Published
2021
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12. Efficient artificial mineralization route to decontaminate Arsenic(III) polluted water -the Tooeleite Way

Author

Malakar, Arindam, Das, Bidisa, Islam, Samirul, Meneghini, Carlo, De Giudici, Giovanni, Merlini, Marco, 'ko, Yury V Kolen, Iadecola, Antonella, Aquilanti, Giuliana, Acharya, Somobrata, and Ray, Sugata

Subjects
Condensed Matter - Materials Science
Abstract

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.

Published
2016
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13. New Mn and V-rich Phosphate Fluoride Obtained by Topochemical Reaction for Na-ion Batteries Positive Electrode

Author

Minart, Gaël, Duttine, Mathieu, Iadecola, Antonella, Salvetat, Jean-Paul, Weill, François, Buffière, Sonia, Wernert, Romain, Olchowka, Jacob, and Croguennec, Laurence

Abstract

A new positive electrode material, Na2.85Mn0.4V1.6(PO4)2F2.4O0.6, is synthesized via a topochemical reaction in an ionic liquid medium, starting with a tailored precursor Mn0.2(VO)0.8PO4·2H2O. Its structural and chemical characterization was conducted using a comprehensive set of techniques including X-ray diffraction, X-ray absorption, and electron paramagnetic resonance spectroscopies, as well as inductively coupled plasma optical emission spectroscopy and electron probe microanalysis. These analyses not only allowed to determine the composition and structure but also shed light on the synthesis reaction mechanism. The resulting active material exhibits promising electrochemical performance, delivering a high capacity of 108 mA h/g at a rate of C/20 with an average potential of 3.75 V vs Na+/Na. Even at a higher rate of 1C, a specific capacity of 90 mA h/g is maintained and an excellent capacity retention of 94% is demonstrated after 200 cycles at C/5. In addition, XAS analysis conducted on materials recovered at different states of charge reveals the redox activity of both manganese and vanadium centers. More generally, this work showcases the feasibility of synthesizing stable Na-deficient polyanionic phases within the NazMnxV2–x(PO4)2F3–yOy(0 ≤ x, y≤ 2, and z≤ 3.6) material family.

Published
2024
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15. Temperature dependent local atomic displacements in Ru substituted SmFe_{1-x}Ru_{x}AsO_{0.85}F_{0.15} superconductors

Author

Joseph, Boby, Iadecola, Antonella, Simonelli, Laura, Maugeri, Laura, Martinelli, Alberto, Palenzona, Andrea, Putti, Marina, and Saini, Naurang L.

Subjects
Condensed Matter - Superconductivity
Abstract

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$2.42 \AA), different from the Fe-As distance ($\sim$2.39 \AA), does not show any change in its force constant with the Ru substitution. These observations suggest that the SmFe$_{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.

Published
2013
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16. Zn Distribution and Chemical Speciation in Marine Biominerals: An Example on Bivalve and Foraminifera Shells from Polluted Sites

Author

De Giudici, Giovanni, primary, Meneghini, Carlo, additional, Buosi, Carla, additional, Carlomagno, Ilaria, additional, Aquilanti, Giuliana, additional, Araki, Tohru, additional, Bedolla, Diana E., additional, Casu, Maria Antonietta, additional, Cherchi, Antonietta, additional, Gianoncelli, Alessandra, additional, Iadecola, Antonella, additional, Kuncser, Andrei C., additional, Maraloiu, V. Adrian, additional, Mathon, Olivier, additional, Rimondi, Valentina, additional, Zuddas, Pierpaolo, additional, and Medas, Daniela, additional

Published
2021
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17. Large local disorder in the superconducting K_{0.8}Fe_{1.6}Se_{2} studied by extended x-ray absorption fine structure

Author

Iadecola, Antonella, Joseph, Boby, Simonelli, Laura, Puri, Alessandro, Mizuguchi, Yoshikazu, Takeya, Hiroyuki, Takano, Yoshihiko, and Saini, Naurang Lal

Subjects
Condensed Matter - Superconductivity, Physics - Chemical Physics
Abstract

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/\AA^{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/\AA^{2}) in comparison to the binary FeSe (k ~ 3.5 eV/\AA^{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.

Published
2012
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18. Temperature dependent local structure of NdFeAsO1-xFx system using arsenic K-edge extended x-ray absorption fine structure

Author

Joseph, Boby, Iadecola, Antonella, Malavasi, Lorenzo, and Saini, Naurang L.

Subjects
Condensed Matter - Superconductivity
Abstract

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., Comment: http://iopscience.iop.org/0953-8984/23/26/265701/

Published
2011
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22. Incorporation of Fe3+ into MnO2 birnessite for enhanced energy storage: impact on the structure and the charge storage mechanisms.

Author

Invernizzi, Ronan, Kovrugin, Vadim M., Molinié, Louise, Iadecola, Antonella, Duttine, Mathieu, Bourgeois, Lydie, Olchowka, Jacob, and Guerlou-Demourgues, Liliane

Abstract

Birnessite δ-MnO2, with its low cost, high theoretical capacity, and stable cycling performance in aqueous electrolytes, holds promise as an electrode material for high-power and cost-effective electrochemical energy storage devices. To address its poor electronic conductivity, we incorporated environmentally friendly iron into birnessite and conducted a comprehensive study on its influence on crystal structure, electrochemical reaction mechanisms, and energy storage performance. In this study, a series of birnessite samples with varying iron content (δ-Mn1−xFexO2 with 0 ≤ x ≤ 0.20) were synthesized using solid-state reactions, resulting in well-crystallized particles with micrometric platelet morphology. Through X-ray absorption and Mössbauer spectroscopies, we clearly demonstrated that Fe replaces Mn in the metal oxide layer, while X-ray diffraction revealed that iron content significantly affects interlayer site symmetry and the resulting polytype. The sample with the lowest iron content (δ-Mn0.96Fe0.04O2) exhibits a monoclinic birnessite structure with an octahedral interlayer site (O-type phase), while increasing iron content leads to hexagonal symmetry with prismatic interlayer sites (P-type phase). Electrochemical investigations indicated that these prismatic sites facilitate the diffusion of partially hydrated alkaline ions and exhibit superior rate capabilities compared to the O-type phase. Furthermore, operando XAS revealed that Fe is electrochemically inactive and that the charge storage in birnessite-type phases in a 0.5 M K2SO4 electrolyte primarily relies on the redox reaction of Mn. Finally, we determined that P-type δ-Mn0.87Fe0.13O2 achieved the best compromise between enhancing electrical conductivity and maintaining a maximum content of electrochemically active Mn cations. [ABSTRACT FROM AUTHOR]

Published
2024
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31. Controlling the Cathodic Potential of KVPO4F through Oxygen Substitution

Author

Wernert, Romain, primary, Nguyen, Long H. B., additional, Petit, Emmanuel, additional, Camacho, Paula Sanz, additional, Iadecola, Antonella, additional, Longo, Alessandro, additional, Fauth, François, additional, Stievano, Lorenzo, additional, Monconduit, Laure, additional, Carlier, Dany, additional, and Croguennec, Laurence, additional

Published
2022
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32. Ordering of a Nanoconfined Water Network around Zinc Ions Induces High Proton Conductivity in Layered Titanate

Author

Kang, Seongkoo, primary, Reeves, Kyle G., additional, Aguilar, Ivette, additional, Porras Gutierrez, Ana Gabriela, additional, Badot, Jean-Claude, additional, Durand-Vidal, Serge, additional, Legein, Christophe, additional, Body, Monique, additional, Iadecola, Antonella, additional, Borkiewicz, Olaf J., additional, Dubrunfaut, Olivier, additional, Fayon, Franck, additional, Florian, Pierre, additional, and Dambournet, Damien, additional

Published
2022
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35. Chemical Design of IrS2 Polymorphs to Understand the Charge/Discharge Asymmetry in Anionic Redox Systems

Author

Marchandier, Thomas, primary, Mariyappan, Sathiya, additional, Abakumov, Artem M., additional, Jobic, Stéphane, additional, Humbert, Bernard, additional, Mevellec, Jean-Yves, additional, Rousse, Gwenaëlle, additional, Avdeev, Maxim, additional, Dedryvère, Rémi, additional, Foix, Dominique, additional, Iadecola, Antonella, additional, Doublet, Marie-Liesse, additional, and Tarascon, Jean-Marie, additional

Published
2021
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36. Charge Storage Mechanism of Li x WO 3 Hexagonal Tungsten Bronze in Aqueous Electrolytes.

Author

Espinosa-Angeles, Julio César, Quarez, Eric, Mvele Eyé'a, Louis-Béni, Douard, Camille, Iadecola, Antonella, Shao, Hui, Taberna, Pierre-Louis, Simon, Patrice, Crosnier, Olivier, and Brousse, Thierry

Subjects
TUNGSTEN bronze, AQUEOUS electrolytes, QUARTZ crystal microbalances, X-ray absorption, X-ray spectroscopy, CRYSTAL structure
Abstract

The electrochemical behavior of the lithium hexagonal tungsten bronze, LixWO3, is investigated herein. The material was synthesized at a low temperature under hydrothermal conditions, yielding nanorod-like particles with growth along the c-axis. Upon cycling in a 5 M LiNO3 aqueous electrolyte, a specific capacity of 71 C.g−1 was obtained at 2 mV.s−1, corresponding to a charge/discharge cycle of 10 min. The charge storage mechanism was elucidated using various complementary techniques, such as electrochemical quartz crystal microbalance (EQCM) and synchrotron operando X-ray absorption spectroscopy (XAS). A desolvation process upon Li+ intercalation into the lattice of the material was evidenced, accompanied by a reversible reduction/oxidation of tungsten cations in the crystal structure upon charge/discharge cycling. [ABSTRACT FROM AUTHOR]

Published
2023
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39. Synthesis of silica-polymer core-shell hybrid materials with enhanced mechanical properties using a new bifunctional silane-based photoinitiator as coupling agent

Author

Haouari, Chérazade, Squires, Alexander, Berthelot, Romain, Stievano, Lorenzo, Sougrati, Moulay Tahar, Morgan, Benjamin, Lebedev, Oleg, Iadecola, Antonella, Borkiewicz, Olaf, Dambournet, Damien, Laboratoire catalyse et spectrochimie (LCS), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Matériaux Polymères Interfaces Environnement Marin - EA 4323 (MAPIEM), Université de Toulon (UTLN), Russian Academy of Sciences [Moscow] (RAS), Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry (IBCh RAS), Laser Zentrum Hannover e.V. (LZH), Sechenov First Moscow State Medical University, Department of Chemical Sciences, University of Messina, Department of Advanced Materials for Energy, Catalonia Institute for Energy Research (IREC), University of Antwerp (UA), Dipartimento di Fisica e Astronomia 'Galileo Galilei', Università degli Studi di Padova = University of Padua (Unipd), CIC NanoGUNE BRTA, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), University of Bath [Bath], The Faraday Institution, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Argonne National Laboratory [Lemont] (ANL), PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Public Health Expertise [Paris, France], Centre National de la Recherche Scientifique (CNRS)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Université de Caen Normandie (UNICAEN), Normandie Université (NU), École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), and Normandie Université (NU)-Institut de Chimie du CNRS (INC)

Subjects
Acrylate polymer, Materials science, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Materials Chemistry, [CHIM]Chemical Sciences, General Materials Science, Bifunctional, Polymer, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, Core-shell, Silica, 021001 nanoscience & nanotechnology, Silane, Hybrid, 0104 chemical sciences, Coupling-agent, Silanol, Photopolymer, chemistry, Chemical engineering, Mechanics of Materials, 0210 nano-technology, Hybrid material, Photoinitiator
Abstract

International audience; Here, we report the use of new bifunctional silane-based type-1 photoinitiator (SPI-1) as a coupling agent for photopolymer filler and silica grafting. The SPI-1 is grafted on the surface of silica nanoparticles via interactions between the ethoxy group of the silane and the silanol groups of the silica surface. The grafted particles are then dispersed or embedded in/with acrylate polymer by a direct photopolymerization process. The materials were characterized using different techniques including UV–vis spectroscopy, FTIR, TGA, and TEM. Their mechanical properties and the surface morphology were also investigated using AFM and DMA analyses. A significant change and enhancement of the mechanical properties of the newly synthesized materials were observed with respect to that of the unmodified silica. The analysis of the morphology at the microscale level reveals interesting information on the origin of this enhancement and on the dispersion of the filler in the polymer matrix.

Published
2021

42. Sputtered multi-cationic oxides thin-films, a new approach for micro-supercapacitors electrodes

Author

Buvat, Gaëtan, Jolayemi, Bukola, Iadecola, Antonella, Blanchard, Florent, Brousse, Thierry, Roussel, Pascal, Lethien, Christophe, Institut d’Électronique, de Microélectronique et de Nanotechnologie - UMR 8520 (IEMN), Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL), Circuits Systèmes Applications des Micro-ondes - IEMN (CSAM - IEMN ), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Centrale Lille-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Université Polytechnique Hauts-de-France (UPHF)-JUNIA (JUNIA), Unité de Catalyse et Chimie du Solide - UMR 8181 (UCCS), Université d'Artois (UA)-Centrale Lille-Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), no information, Renatech Network, CMNF, and Université de Lille, LillOA

Subjects
[CHIM.INOR] Chemical Sciences/Inorganic chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, ComputingMilieux_MISCELLANEOUS
Abstract

International audience

Published
2021

48. A combined operando synchrotron X-ray absorption spectroscopy and first-principles density functional theory study to unravel the vanadium reedox paradox in the Na3V2(PO4)2F3–Na3V2(PO4)2FO2 compositions

Author

Nguyen, Long H. B., Iadecola, Antonella, Belin, Stéphanie, Olchowka, Jacob, Masquelier, Christian, Carlier, Dany, Croguennec, Laurence, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), The authors thank the RS2E Network for the funding of LHBN’s Ph.D. thesis as well as the financial support of Région Nouvelle Aquitaine, the French National Research Agency (STORE-EX Labex Project ANR-10-LABX-76-01), and the European Union’s Horizon 2020 research and innovation program under grant agreement no. 646433-NAIADES. XAS experiments were performed on the ROCK beamline at SOLEIL synchrotron, which is benefiting from a public grant overseen by the French National Research Agency as part of the 'Investissements d’Avenir' program (reference: ANR-10-EQPX-45). The Mésocentre de Calcul Intensif Aquitain (MCIA) and the modeling center of ISM are acknowledged for computing facilities., 2020-152, ANR-10-EQPX-0045,ROCK,Spectromètre EXAFS Rapide pour Cinétiques Chimiques(2010), ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
[CHIM.MATE]Chemical Sciences/Material chemistry
Abstract

International audience; The redox processes involved in the Na+ deintercalation from Na3V2(PO4)2F3, Na3V2(PO4)2F2O, and Na3V2(PO4)2F1.5O1.5 are investigated operando by synchrotron X-ray absorption spectroscopy at the vanadium K-edge. A continuous evolution in the pre-edge and edge regions is observed for the three compositions, which is in good agreement with a progressive oxidation of vanadium. In the oxygen-substituted compositions, Na3V2(PO4)2F2O and Na3V2(PO4)2F1.5O1.5, the F–V3+O4–F and F–V4+O4═O redox centers coexist and can be simultaneously activated owing to the reverse inductive effect promoted by the presence of highly covalent vanadyl bonds on V4+ sites. Principal component analysis of the dataset collected operando for the three compositions is performed. It reveals that three independent spectra, corresponding to different charge orderings on vanadium sites at different states of charge, are required to describe these three systems. Furthermore, the extended X-ray absorption fine structure analysis of the principal components is performed in order to gain insightful information on the evolution of the vanadium local environment upon cycling. By the use of first-principles density functional theory calculations, we demonstrate that the potential step observed in all Na2V2(PO4)2F3–yOy compositions is related to a charge ordering on vanadium sites with a preferential oxidation of vanadium ions in the same bioctahedra.

Published
2020

50. An Original Empirical Method for Simulating V L2,3Edges: The Example of KVPO4F and KVOPO4Cathode Materials

Author

Longo, Alessandro, Wernert, Romain, Iadecola, Antonella, Sahle, Christoph J., Stievano, Lorenzo, Croguennec, Laurence, Carlier, Dany, and Mirone, Alessandro

Abstract

Reversible chemical reactions are the most common mechanism storing electrochemical energy in M-ion batteries (M = Li, Na, K....). At the positive electrode, these transformations consist in the solid-state oxidation or reduction of transition metal ions going along with the reversible (de)intercalation of an alkali cation from the crystal structure. X-ray spectroscopies are among the most suitable tools to unveil and monitor these reactions. The interpretation of experimental spectra, however, is not trivial. This is particularly true in V-based positive electrodes since the variety of oxidation states of vanadium as well as its coordination and bonding geometries may lead to complex spectroscopic features that call for ab initiomodeling to understand the spectra. Here we show not only that V L2,3-edge X-ray Raman spectra can effectively be modeled by a full ab initioapproach but also that the empirically obtained Hamiltonian parameters can reproduce shape and intensity of the experimental spectra from a given coordination geometry. In a broader context, our study shows that inexpensive empirical calculations provide highly reliable information and help solve the electronic structure of transition metal oxides compounds, which governs the electrochemical behavior in M-ion batteries. The promising results shown here underline the efficiency of this strategy for X-ray spectroscopy data analysis, which can be generalized and extended to the wider family of vanadium phosphate-based polyanionic compounds. Such an approach can in principle be extended to any transition metal-based material.

Published
2022
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