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1. Activation of anionic redox in d0 transition metal chalcogenides by anion doping

Author: Bernhard T. Leube, Clara Robert, Dominique Foix, Benjamin Porcheron, Remi Dedryvère, Gwenaëlle Rousse, Elodie Salager, Pierre-Etienne Cabelguen, Artem M. Abakumov, Hervé Vezin, Marie-Liesse Doublet, and Jean-Marie Tarascon
Subjects: Science
Abstract: Activation of anionic redox in battery materials promises great benefits for battery materials, but remains an elusive phenomenon. Here, the authors present anion-doping as a novel strategy to unlock electrochemical activity in the cobalt/nickel free cathode material, Li2TiS3-xSex.
Published: 2021
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2. The Ir–OOOO–Ir transition state and the mechanism of the oxygen evolution reaction on IrO2(110)

Author: Tobias Binninger, Marie-Liesse Doublet, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-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 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)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-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 Paris - Chimie ParisTech-PSL (ENSCP), and Université Fédérale Toulouse Midi-Pyrénées-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )
Subjects: Nuclear Energy and Engineering, Renewable Energy, Sustainability and the Environment, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Environmental Chemistry, Pollution
Abstract: International audience; Carefully assessing the energetics along the pathway of the oxygen evolution reaction (OER), our computational study reveals that the "classical" OER mechanism on the (110) surface of iridium dioxide (IrO 2) must be reconsidered. We find that the OER follows a bi-nuclear mechanism with adjacent top surface oxygen atoms as fixed adsorption sites, whereas the iridium atoms underneath play an indirect role and maintain their saturated 6-fold oxygen coordination at all stages of the reaction. The oxygen molecule is formed, via an Ir-OOOO-Ir transition state, by association of the outer oxygen atoms of two adjacent Ir-OO surface entities, leaving two intact Ir-O entities at the surface behind. This is drastically different from the commonly considered mono-nuclear mechanism where the O 2 molecule evolves by splitting of the Ir-O bond in an Ir-OO entity. We regard the rather weak reducibility of crystalline IrO 2 as the reason for favoring the novel pathway, which allows the Ir-O bonds to remain stable and explains the outstanding stability of IrO 2 under OER conditions. The establishment of surface oxygen atoms as fixed electrocatalytically active sites on a transitionmetal oxide represents a paradigm shift for the understanding of water oxidation electrocatalysis, and it reconciles the theoretical understanding of the OER mechanism on iridium oxide with recently reported experimental results from operando X-ray spectroscopy. The novel mechanism provides an efficient OER pathway on a weakly reducible oxide, defining a new strategy towards the design of advanced OER catalysts with combined activity and stability.
Published: 2022
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3. Chemical Design of IrS2 Polymorphs to Understand the Charge/Discharge Asymmetry in Anionic Redox Systems

Author: Thomas Marchandier, Sathiya Mariyappan, Artem M. Abakumov, Stéphane Jobic, Bernard Humbert, Jean-Yves Mevellec, Gwenaëlle Rousse, Maxim Avdeev, Rémi Dedryvère, Dominique Foix, Antonella Iadecola, Marie-Liesse Doublet, Jean-Marie Tarascon, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Skolkovo Institute of Science and Technology [Moscow] (Skoltech), Institut des Matériaux Jean Rouxel (IMN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - Ecole Polytechnique de l'Université de Nantes (Nantes Univ - EPUN), Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-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 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)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), The University of Sydney, Australian Nuclear Science and Technology Organisation [Australie] (ANSTO), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Collège de France - Chaire Chimie du solide et énergie, Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), U.S. Department of Energy under contract no. DE-AC02-06CH11357European Research Council (ERC) (FP/2014)/ERC grant/project no. 670116-ARPEMA, ANR-10-EQPX-0045,ROCK,Spectromètre EXAFS Rapide pour Cinétiques Chimiques(2010), Chaire Chimie du solide et énergie, Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-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 Paris - Chimie ParisTech-PSL (ENSCP), Université Fédérale Toulouse Midi-Pyrénées-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Sorbonne Université (SU)
Subjects: General Chemical Engineering, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Materials Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, [CHIM.OTHE]Chemical Sciences/Other, 010402 general chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, 01 natural sciences, 0104 chemical sciences
Abstract: International audience; Li-ion batteries are growing in demand and such growth calls for the quest for high-energy-density electrode materials. Li-rich layered oxides that show both cationic and anionic redox are expected to meet the high energy requirement. However, the oxygen anion activity triggers numerous structural and electronic rearrangements that need to be understood prior to envisioning applications. Here, we chemically design two new LixIrS2 polymorphs to further interrogate the mechanisms of the ligand redox process. By combined structural and spectroscopic characterizations, we show that electrochemical lithiation/delithiation of the polymorphs involve different sulfur redox couples that stand as unusual behavior. These structure-dependent kinetic pathways lead to an similar to 1 V difference between the two polymorphs, hence providing the missing link between the structure and hysteresis in anionic redox systems. These insights into the origin of hysteresis can guide proper parameters to cure it, hence laying the groundwork for the design of new practical electrode materials.
Published: 2021
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4. Recent Advances in Theoretical Methodology to Battery Interfaces

Author: Marie-Liesse DOUBLET
Published: 2022
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5. Stacking Versatility in Alkali-Mixed Honeycomb Layered NaKNi2TeO6

Author: Gwenaëlle Rousse, François Weill, François Fauth, Montse Casas-Cabanas, Jon Serrano-Sevillano, Marie-Liesse Doublet, Romain Berthelot, Bernard Fraisse, Dany Carlier, Danielle Laurencin, 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), 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), CIC ENERGIGUNE - Parque Tecnol Alava, 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), CELLS ALBA, Barcelona 08290, Spain, Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ikerbasque - Basque Foundation for Science, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), The BL04-MSPD staff of CELLS-ALBA synchrotron is acknowledged for granting beamtime through InHouse quota (proposal 2020014011)., Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), 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), and Basque Foundation for Science (Ikerbasque)
Subjects: Diffraction, Chemistry, Sodium, Stacking, Honeycomb (geometry), Oxides, Context (language use), [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 021001 nanoscience & nanotechnology, Alkali metal, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Chemical physics, Cations, Potassium, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Density functional theory, Physical and Theoretical Chemistry, Layers, 0210 nano-technology, Stacking fault
Abstract: International audience; The reaction between P2-type honeycomb layered oxides Na2Ni2TeO6 and K2Ni2TeO6 enables the formation of NaKNi2TeO6. The compound is characterized by X-ray diffraction and 23Na solid-state nuclear magnetic resonance spectroscopy, and the structure is discussed through density functional theory calculations. In addition to the honeycomb Ni/Te cationic ordering, NaKNi2TeO6 exhibits a unique example of alternation of sodium and potassium layers instead of a random alkali-mixed occupancy. Stacking fault simulations underline the impact of the successive position of the Ni/Te honeycomb layers and validate the presence of multiple stacking sequences within the powder material, in proportions that evolve with the synthesis conditions. In a broader context, this work contributes to a better understanding of the alkali-mixed layered compounds.
Published: 2021
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6. Triggering Anionic Redox Activity in Li 3 NbS 4 Through Cationic Disordering or Substitution

Author: Thomas Marchandier, Sathiya Mariyappan, Maria A. Kirsanova, Artem M. Abakumov, Gwenaëlle Rousse, Dominique Foix, Moulay‐Tahar Sougrati, Marie Liesse Doublet, Jean‐Marie Tarascon, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Skolkovo Institute of Science and Technology [Moscow] (Skoltech), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-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 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)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Collège de France - Chaire Chimie du solide et énergie, Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), European Project: 670116,H2020,ERC-2014-ADG,ARPEMA(2015), and Chaire Chimie du solide et énergie
Subjects: Renewable Energy, Sustainability and the Environment, crystal- electronic structure relationship, cation substitution, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], [CHIM]Chemical Sciences, Li-ion batteries, General Materials Science, disordered rock-salt phases, [CHIM.MATE]Chemical Sciences/Material chemistry, anionic redox
Abstract: International audience; Extensive utilization of Li-ion batteries for varieties of applications necessitates ceaseless improvements of electrode materials for achieving higher energy density. Towards this goal, Li-rich layered oxides exhibiting high capacity due to cumulated cationic and anionic redox activities are under study for nearly a decade. Still, several unanswered questions remain with respect to these Li-driven anionic redox reactions in terms of the activation process and long-term consequences upon cycling. Here, the Li-rich Li3NbS4 phase is focused, and synthesized as two different polymorphs, namely ordered and disordered phases. From analyses of their chemical and electrochemical properties, a crystal-electronic structure relationship is unraveled that triggers the anionic redox activity in these compounds. Moreover, through complementary theoretical calculations, the capability of cationic disorder to trigger anionic redox activity via the hybridization of cationic and non-bonding anionic energy levels is shown. This finding is further supported by the appearance of anionic redox activity by introducing the disorder through cationic substitution. Altogether, the insights derived can help in designing new anionic redox materials with optimum performances for practical applications.
Published: 2022
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7. Rationalizing the alkali ions distribution along the honeycomb layered (Li,Na)2SnO3 pseudo solid solution

Author: Romain Berthelot, Carla Crobu, Eunice Mumba Mpanga, Bernard Fraisse, Marie-Liesse Doublet, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-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 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)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010)
Subjects: [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Solid solution, Density functional theory calculations, General Materials Science, Honeycomb ordering, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, Physical and Theoretical Chemistry, Alkali transition metal layered oxide, Condensed Matter Physics
Abstract: International audience; Alkali-rich layered oxides Li2SnO3 and Na2SnO3 are isostructural, but no alkali-mixed compositions have been reported so far. While the thermodynamic stability of such mixed compositions is predicted by DFT calculations mainly for the sodium-rich side, single-phase compounds Li2-xNaxSnO3 were successfully obtained in the whole composition range (0 ≤ x ≤ 2) by conventional solid-state synthesis thanks to a quenching procedure at the end of the heat treatment. From Li2SnO3 to Na2SnO2, the evolution of the cell parameters and the DFT calculations demonstrate that the lithium-to-sodium substitution occurs firstly inside the alkali layer up to Li0.5Na1.5SnO3 and then in the honeycomb layer.
Published: 2023
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8. Access to Ru(IV)–Ru(V) and Ru(V)–Ru(VI) Redox in Layered Li 7 RuO 6 via Intercalation Reactions

Author: Haifeng Li, Beata Taudul, Grant C. B. Alexander, Jue Liu, John W. Freeland, Marie-Liesse Doublet, Jordi Cabana, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-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 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)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Argonne National Laboratory [Lemont] (ANL), University of Illinois [Chicago] (UIC), and University of Illinois System
Subjects: General Chemical Engineering, Materials Chemistry, [CHIM]Chemical Sciences, General Chemistry
Abstract: International audience
Published: 2022
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9. New p-type Al-substituted SrSnO3 perovskites for TCO applications?

Author: Rached Ben Hassen, Mouna Ben Yahia, Marie-Liesse Doublet, B. Belgacem, Leila Ben Amor, Jean-Sébastien Filhol, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Unité de Recherche de Chimie des Matériaux (ISSBAT), and Université de Tunis El Manar (UTM)
Subjects: 010302 applied physics, Materials science, Metals and Alloys, chemistry.chemical_element, 02 engineering and technology, General Chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, Oxygen, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, chemistry, 0103 physical sciences, Materials Chemistry, Ceramics and Composites, Valence band, [CHIM]Chemical Sciences, 0210 nano-technology
Abstract: International audience; Novel p-type SrSn 1-x Al x O 3 (x=0, 0.2, 0.5) perovskites are presented as potential candidates for electro-optical applications. A combined experimental and theoretical study reveals that chemical substitutions can be used as a lever to stabilize oxygen holes in the valence band. Transparent conductive oxides (TCO) are an original class of materials combining two contrasting properties in one single compound that is, electrical conductivity and optical transparency in visible spectrum. TCOs are widely used in electro-optical devices such as flat-panels, organic light emitting diodes, photovoltaic devices, and plasma displays. 1-6 However, standard commercial TCOs are limited to post-transition metal oxides, e.g. ZnO, In 2 O 3 and SnO and derivatives. 7 These oxides are characterized by a band gap larger than 3eV between the O(2p) valence band maximum (VBM) and the metal (s,p) conduction band minimum (CBM). They display excellent n-type electronic conductivity when the donor, i.e. metal, is doped. In contrast, the development of high performant p-type TCOs is more challenging, 8-11 due to the strongly localized states of the acceptor, i.e. oxygen, which are at the origin of large hole effective mass (poor electronic conductivity). As a consequence, the probability is high that the newly created shallow acceptors are counterbalanced by the formation of native defects such as anion vacancies or cation interstice. 12 Up to now, n-type tin-doped indium oxide (ITO) shows the best performance. 1,13 Nevertheless and despite the remarkable properties of ITO, the relative high cost of In and its increasing scarcity appeals for alternative elements or materials. 14 ABO 3 perovskites are of great interest thanks to the use of mixed A and B cations capable of generating versatile structures and properties with high chemical stability. SrSnO 3 (SSO) is one of the most promising candidate due to its high visible light transmittance, high thermal stability and reasonable cost. 15 Pure SSO is a charge transfer insulator crystallizing in the orthorhombic GdFeO 3-type structure with lattice parameters a = 5.7113 Å, b = 8.0647 Å and c = 5.7042 Å. In this tri-dimensional structure, SnO 6 octahedra are corner-shared and Sr lies in the available vacant interstices. 16,17 To meet the industrial specifications of efficient TCOs, SSO must display high carrier concentration and mobility 18-21 which requires its doping. Attempts to develop n-type SSO candidates that could rival the electro-optical properties of ITO were intensively described and interesting performance were reported. 22-26 In contrast, p-type doping is still lacking for this class of materials. 27-29 Recently, Hautier et al. showed that the large difference in mobility between n-type and p-type materials is not inevitable and could be overcome by the investigation of alternative chemistries. Based on this statement and considering the high industrial stakes associated with the discovery of new p-type TCOs, we used chemical substitution to check the ability of SSO to behave as a performant p-type TCO. This concept was introduced for the first time by Hosono and coworkers 2 and is known as the "chemical modulation of the valence band" (CMVB). Based on the hypothesis that partial substitution of Sn(IV) for the smaller trivalent cation Al(III) can enhance electron delocalization (through a significant volume contraction of the perovskite structure) while concomitantly generate stable holes in the valence band, various Sn/Al-substituted SSO phases were synthesized. Using X-ray diffraction (XRD) and Scanning Electron Microscopy (SEM) equipped with Energy Dispersive X-ray Spectroscopy (EDX), we here demonstrate the solubility of the Al element in the SSO perovskite structure for SrSn 1-x Al x O 3 (SSAO) compositions x = 0 to 0.5. UV-Vis-NIR spectroscopy is then used to show that the absorption profile of SSO is not altered by the chemical Sn/Al substitution while the low-energy absorption band (intra-band transitions) is enhanced. A thermodynamic study based on first-principles DFT (Density Functional Theory) calculations is then performed to determine the type of charge carriers in SSO and SSAOs (p-type) and combined with chemical bond analyses to rationalize the impact of Sn/Al substitution on the p-type performance of SSAOs. SrSn 1-x Al x O 3 (x= 0, 0.2, 0.5) perovskites were successfully obtained through solid state reaction. Details of the synthesis steps are given in ESI part. The impact of the Sn(IV)/Al(III) substitution ratio on the macroscopic properties of SrSn 1-x Al x O 3 was investigated through complementary XRD and SEM-EDX. The structural and morphological analyses of the synthesized samples are presented in Fig.1 and S1. From the XRD patterns of SSO and SrSn 1-x Al x O 3 (SSAO) the orthorhombic Pnma structure (JCPDS 10-6354) is confirmed. A slight shift towards higher angles is observed in agreement with the smaller Shannon ionic radius of Al 3+ (0.54 Å) compared to Sn 4+ (0.69 Å).
Published: 2020
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10. Advancement of the Homogeneous Background Method for the Computational Simulation of Electrochemical Interfaces

Author: Arthur Hagopian, Marie-Liesse Doublet, Jean-Sébastien Filhol, and Tobias Binninger
Subjects: Condensed Matter - Materials Science, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, Physical and Theoretical Chemistry, Computational Physics (physics.comp-ph), Physics - Computational Physics, Computer Science Applications
Abstract: Computational studies of electrochemical interfaces based on density-functional theory (DFT) play an increasingly important role in present research on electrochemical processes for energy conversion and storage. The homogeneous background method (HBM) offers a straightforward approach to charge the electrochemical system within DFT simulations, but it typically requires the specification of the "active" fraction of excess electrons based on a certain choice of the electrode-electrolyte boundary location, which can be difficult in presence of electrode-surface adsorbates or explicit solvent molecules. In this work, we present a methodological advancement of the HBM, both facilitating and extending its applicability. The advanced version neither requires energy corrections nor the specification of the "active" fraction of excess electrons, providing a versatile and readily available method for the simulation of charged interfaces also when adsorbates or explicit solvent molecules are present. Our computational DFT results for Pt(111), Au(111) and Li(100) metal electrodes in high-dielectric-constant solvents demonstrate an excellent agreement in the interfacial charging characteristics obtained from simulations with the advanced HBM in comparison with the (linearized) Poisson-Boltzmann model (PBM).
Published: 2022

11. The Electrochemical Sodiation of Sb Investigated by Operando X-ray Absorption and 121Sb Mössbauer Spectroscopy: What Does One Really Learn?

Author: Ali Darwiche, Marcus Fehse, Abdelfattah Mahmoud, Camille La Fontaine, Bernard Fraisse, Raphael P. Hermann, Marie-Liesse Doublet, Laure Monconduit, Moulay T. Sougrati, Mouna Ben Yahia, and Lorenzo Stievano
Subjects: X-ray absorption spectroscopy, Mössbauer spectroscopy, DFT calculations, chemometrics, MCR-ALS, Na-ion batteries, alloy reaction, Sb, Production of electric energy or power. Powerplants. Central stations, TK1001-1841, Industrial electrochemistry, TP250-261
Abstract: In this study, we want to highlight the assets and restrictions of X-ray absorption spectroscopy (XAS) and Mössbauer spectroscopy for investigating the mechanism of the electrochemical reaction of antimony electrode materials vs. Na. For this, operando XAS was carried out during the first one and a half cycles, and the whole set of measured data was analysed using a statistical-chemometric approach, while low temperature Mössbauer spectroscopy measurements were carried out ex situ on selected samples stopped at different points of the electrochemical reaction. Complementary ab initio calculations were performed to support the experimental findings. Both techniques show that, upon the first sodiation, most Sb reacts with Na to form disordered Na 3 Sb. This step is accompanied by the formation of amorphous Sb as an intermediate. Upon inversion of the current Na 3 Sb is desodiated and an amorphous Sb phase, distinct from the pristine bulk Sb state, is gradually formed. However, both XAS and Mössbauer spectroscopy were unable to spot the formation of intermediate Na x Sb phases, which were evinced in previous works by operando Pair Distribution Function analyses. The results shown here clearly assign such failure to the intrinsic inability of both techniques to identify these intermediates.
Published: 2018
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12. (Digital Presentation) Elucidation of Active Oxygen Sites upon Delithiation of Li3IrO4

Author: Haifeng Li, Arnaud Perez, Teak Boyko, John Freeland, Marie-Liesse Doublet, and Jordi Cabana
Abstract: Transformational increases in the storage capacity of battery cathodes could be achieved by tapping into the redox activity at oxide ligands in addition to conventional transition metal couples. Yet the key signatures that govern such lattice oxygen redox (LOR) have not been ascertained. Li3IrO4 has the largest reversible LOR, rendering it a unique model system. Here, X-ray spectroscopy and computational simulations reveal that LOR in Li3IrO4 is selectively compensated via O sites with 3 lone pairs, which are activated by Li/Ir disorder. The 2-electron LOR can be reversed to regenerate the initial state without unlocking competing bulk reactions observed in many other compounds. We uncover an intricate interplay between stoichiometry, O coordination and non-bonding states in LOR and pinpoint spectroscopic signatures. This interplay is indispensable to design materials with 3d metals that fulfill the promise of LOR to overcome the bottlenecks of current cathodes for future implementation in practical batteries.
Published: 2022
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13. Investigation of alkali and alkaline earth solvation structures in tetraglyme solvent

Author: T. Picard, Jean-Sébastien Filhol, N. Sergent, Long H. B. Nguyen, Christophe Raynaud, Marie-Liesse Doublet, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Matériaux Interfaces ELectrochimie (MIEL), Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI), Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), 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), 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), 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 ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)
Subjects: Materials science, Metal ions in aqueous solution, Implicit solvation, Solvation, General Physics and Astronomy, 02 engineering and technology, Electrolyte, 010402 general chemistry, 021001 nanoscience & nanotechnology, Alkali metal, 01 natural sciences, 0104 chemical sciences, Solvation shell, Chemical physics, Molecular vibration, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Molecule, Physical and Theoretical Chemistry, 0210 nano-technology
Abstract: International audience; This study compares molecular calculations performed with molecular and periodic codes through an investigation of the solvation structures of alkali and alkaline earth metal ions in tetraglyme solution. The two codes are able to produce equivalent structural and energetic information at the same level of theory, and in the presence of the implicit solvation model or not. This comparison reveals that molecular optimisations can be performed with periodic codes and used directly as input models for interface or electrochemistry calculations in order to preserve the solvent−solute interaction and the cavitation energy. By a rigorous comparison, we have demonstrated that equivalent energetic values can be obtained with the conventional PBE-D3 and the newly developed SCAN-rVV10 functional. Nevertheless, when the vibrational features are concerned and when the molecule possesses a highly conjugated system, the SCAN-rVV10 functional is required to describe the vibrational modes properly. The computed IR/Raman spectra can thus be used as essential information to determine the first solvation shell of metal ions in glyme-based solutions. In tetraglyme solution, the alkali and alkaline earth metal ions exhibit a diverse solvation structure. Small ions like Li+ and Mg2+ tend to adopt a coordination number of five or six, while larger ions, Na+, K+, and Ca2+, prefer an eight-coordinated environment, and the metal−ligand interaction increases in the order K+−O < Na+−O < Li+−O < Ca2+−O < Mg2+−O. The solvation spheres play a significant role in the stability and the reactivity of the solvated ions, and can thus be used as input models to construct the solvation structure in more sophisticated electrolytes, such as polyethylene oxide, or perform electrochemical calculations.
Published: 2021
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14. Activation of anionic redox in d0 transition metal chalcogenides by anion doping

Author: Jean-Marie Tarascon, Artem M. Abakumov, Dominique Foix, Marie-Liesse Doublet, Elodie Salager, Rémi Dedryvère, Bernhard T. Leube, Hervé Vezin, Clara Robert, Gwenaëlle Rousse, Pierre-Etienne Cabelguen, Benjamin Porcheron, Université de Lille, CNRS, Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 [LASIRE], Collège de France (CdF (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), 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), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), European Project: 670116,H2020,ERC-2014-ADG,ARPEMA(2015), 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), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL), and Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516
Subjects: inorganic chemicals, Materials science, Science, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, 7. Clean energy, Redox, General Biochemistry, Genetics and Molecular Biology, Ion, Transition metal, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Twist, Multidisciplinary, Doping, Cationic polymerization, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Electron localization function, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, [CHIM.POLY]Chemical Sciences/Polymers, 0210 nano-technology
Abstract: Expanding the chemical space for designing novel anionic redox materials from oxides to sulfides has enabled to better apprehend fundamental aspects dealing with cationic-anionic relative band positioning. Pursuing with chalcogenides, but deviating from cationic substitution, we here present another twist to our band positioning strategy that relies on mixed ligands with the synthesis of the Li2TiS3-xSex solid solution series. Through the series the electrochemical activity displays a bell shape variation that peaks at 260 mAh/g for the composition x = 0.6 with barely no capacity for the x = 0 and x = 3 end members. We show that this capacity results from cumulated anionic (Se2−/Sen−) and (S2−/Sn−) and cationic Ti3+/Ti4+ redox processes and provide evidence for a metal-ligand charge transfer by temperature-driven electron localization. Moreover, DFT calculations reveal that an anionic redox process cannot take place without the dynamic involvement of the transition metal electronic states. These insights can guide the rational synthesis of other Li-rich chalcogenides that are of interest for the development of solid-state batteries.
Published: 2021
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15. Correlating ligand-to-metal charge transfer with voltage hysteresis in a Li-rich rock-salt compound exhibiting anionic redox

Author: Artem M. Abakumov, Rémi Dedryvère, Gwenaëlle Rousse, Jean-Marie Tarascon, Marie-Liesse Doublet, Moulay Tahar Sougrati, Anatoliy Senyshyn, Biao Li, Antonella Iadecola, Anatolii V. Morozov, Leiting Zhang, Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), and Collège de France (CdF (institution))
Subjects: General Chemical Engineering, Salt (chemistry), 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Redox, law.invention, Metal, law, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Lone pair, chemistry.chemical_classification, Chemistry, Ligand, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Cathode, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Hysteresis, [CHIM.POLY]Chemical Sciences/Polymers, Octahedron, Chemical physics, visual_art, visual_art.visual_art_medium, 0210 nano-technology
Abstract: Anionic redox is a double-edged sword for Li-ion cathodes because it offers a transformational increase in energy density that is also negated by several detrimental drawbacks to its practical implementation. Among them, voltage hysteresis is the most troublesome because its origin is still unclear and under debate. Herein, we tackle this issue by designing a prototypical Li-rich cation-disordered rock-salt compound Li1.17Ti0.33Fe0.5O2 that shows anionic redox activity and exceptionally large voltage hysteresis while exhibiting a partially reversible Fe migration between octahedral and tetrahedral sites. Through combined in situ and ex situ spectroscopic techniques, we demonstrate the existence of a non-equilibrium (adiabatic) redox pathway enlisting Fe3+/Fe4+ and O redox as opposed to the equilibrium (non-adiabatic) redox pathway involving sole O redox. We further show that the charge transfer from O(2p) lone pair states to Fe(3d) states involving sluggish structural distortion is responsible for voltage hysteresis. This study provides a general understanding of various voltage hysteresis signatures in the large family of Li-rich rock-salt compounds. The use of anionic redox chemistry in high-capacity Li-rich cathodes is being hampered by voltage hysteresis, the origin of which remains obscure. Now it has been shown that sluggish ligand-to-metal charge transfer kinetically traps an intermediate Fe4+ species and is responsible for voltage hysteresis in the prototypical Li-rich cation-disordered rock-salt Li1.17Ti0.33Fe0.5O2.
Published: 2021
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16. Stacking Versatility in Alkali-Mixed Honeycomb Layered NaKNi

Author: Romain, Berthelot, Jon, Serrano-Sevillano, Bernard, Fraisse, François, Fauth, François, Weill, Danielle, Laurencin, Montse, Casas-Cabanas, Dany, Carlier, Gwenaëlle, Rousse, and Marie-Liesse, Doublet
Abstract: The reaction between P2-type honeycomb layered oxides Na
Published: 2021

17. Charge Transfer Band Gap as an Indicator of Hysteresis in Li-Disordered Rock Salt Cathodes for Li-Ion Batteries

Author: Antonella Iadecola, Matthieu Saubanère, Marie-Liesse Doublet, Jean-Marie Tarascon, Jordi Cabana, Haifeng Li, Quentin Jacquet, Gwenaëlle Rousse, Erik J. Berg, 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), Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), University of Illinois [Chicago] (UIC), University of Illinois System, Paul Scherrer Institute (PSI), 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), Collège de France - Chaire Chimie du solide et énergie, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and 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)
Subjects: chemistry.chemical_classification, Band gap, Chemistry, Cationic polymerization, Salt (chemistry), Charge (physics), General Chemistry, 010402 general chemistry, 01 natural sciences, Biochemistry, Redox, Catalysis, Cathode, 0104 chemical sciences, law.invention, Ion, Hysteresis, Colloid and Surface Chemistry, law, Chemical physics, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], ComputingMilieux_MISCELLANEOUS
Abstract: Disordered rock salt cathodes showing both anionic and cationic redox are being extensively studied for their very high energy storage capacity. Mn-based disordered rock salt compounds show much higher energy efficiency compared to the Ni-based materials as a result of the different voltage hysteresis, 0.5 and 2 V, respectively. To understand the origin of this difference, we herein report the design of two model compounds, Li
Published: 2019
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18. Unlocking anionic redox activity in O3-type sodium 3d layered oxides via Li substitution

Author: Marie-Liesse Doublet, Anatolii V. Morozov, Benjamin Porcheron, Mohamed Chakir, Young-Sang Yu, Leiting Zhang, Artem M. Abakumov, Maxim Avdeev, Wanli Yang, Jordi Cabana, Sathiya Mariyappan, Jean-Marie Tarascon, Michaël Deschamps, Jinpeng Wu, Rémi Dedryvère, Gwenaëlle Rousse, Wang Qing, Collège de France (CdF (institution)), 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), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Université d'Orléans (UO), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), ANR-10-EQPX-0045,ROCK,Spectromètre EXAFS Rapide pour Cinétiques Chimiques(2010), European Project: 670116,H2020,ERC-2014-ADG,ARPEMA(2015), 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), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), and Collège de France - Chaire Chimie du solide et énergie
Subjects: Materials science, Sodium, chemistry.chemical_element, 02 engineering and technology, Manganese, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Redox, Na-ion batteries, Affordable and Clean Energy, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Phase (matter), General Materials Science, Nanoscience & Nanotechnology, water-stable, Mechanical Engineering, cation migration, Cationic polymerization, General Chemistry, O3-type layered oxide, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Mechanics of Materials, Electrode, Density functional theory, 0210 nano-technology, anionic redox, Stoichiometry
Abstract: Sodium ion batteries, because of their sustainability attributes, could be an attractive alternative to Li-ion technology for specific applications. However, it remains challenging to design high energy density and moisture stable Na-based positive electrodes. Here, we report an O3-type NaLi1/3Mn2/3O2 phase showing anionic redox activity, obtained through a ceramic process by carefully adjusting synthesis conditions and stoichiometry. This phase shows a sustained reversible capacity of 190 mAh g−1 that is rooted in cumulative oxygen and manganese redox processes as deduced by combined spectroscopy techniques. Unlike many other anionic redox layered oxides so far reported, O3-NaLi1/3Mn2/3O2 electrodes do not show discernible voltage fade on cycling. This finding, rationalized by density functional theory, sheds light on the role of inter- versus intralayer 3d cationic migration in ruling voltage fade in anionic redox electrodes. Another practical asset of this material stems from its moisture stability, hence facilitating its handling and electrode processing. Overall, this work offers future directions towards designing highly performing sodium electrodes for advanced Na-ion batteries. Sodium ion batteries could be an attractive alternative to Li-ion technology but designing high energy density and moisture stable Na-based cathodes is challenging. Adjusting synthesis conditions and stoichiometry, an O3-type NaLi1/3Mn2/3O2 phase with anionic redox activity is reported.
Published: 2021
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19. Correlating ligand-to-metal charge transfer with voltage hysteresis in a Li-rich rock-salt compound exhibiting anionic redox

Author: Biao, Li, Moulay Tahar, Sougrati, Gwenaëlle, Rousse, Anatolii V, Morozov, Rémi, Dedryvère, Antonella, Iadecola, Anatoliy, Senyshyn, Leiting, Zhang, Artem M, Abakumov, Marie-Liesse, Doublet, and Jean-Marie, Tarascon
Abstract: Anionic redox is a double-edged sword for Li-ion cathodes because it offers a transformational increase in energy density that is also negated by several detrimental drawbacks to its practical implementation. Among them, voltage hysteresis is the most troublesome because its origin is still unclear and under debate. Herein, we tackle this issue by designing a prototypical Li-rich cation-disordered rock-salt compound Li
Published: 2020

20. Unveiling Pseudocapacitive Charge Storage Behavior in FeWO 4 Electrode Material by Operando X‐Ray Absorption Spectroscopy

Author: Antonella Iadecola, Christophe Payen, Richard Retoux, Marie-Liesse Doublet, Etsuro Iwama, Katsuhiko Naoi, Frédéric Favier, Thierry Brousse, Nicolas Goubard-Bretesché, Camille Douard, Kazuaki Kisu, Olivier Crosnier, 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), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), 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)-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), 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), Tokyo University of Agriculture and Technology (TUAT), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), 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), 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), Normandie Université (NU)-Institut de Chimie du CNRS (INC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)
Subjects: Materials science, Pseudocapacitance 2, Absorption spectroscopy, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Redox, Pseudocapacitance, law.invention, Biomaterials, Metal, law, FeWO 4, General Materials Science, Operando, X-ray absorption spectroscopy, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Capacitor, Chemical physics, visual_art, Electrode, visual_art.visual_art_medium, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, Electrochemical capacitors, Biotechnology
Abstract: International audience; In nano-sized FeWO 4 electrode material, both Fe and W metal cations are suspected to be involved in the fast and reversible Faradaic surface reactions giving rise to its pseudocapacitive signature. As for any other pseudocapacitive materials, to fully understand the charge storage mechanism, a deeper insight into the involvement of the electroactive cations still has to be provided. The present paper illustrates how operando X-ray absorption spectroscopy (XAS) has been successfully used to collect data of unprecedented quality allowing to elucidate the complex electrochemical behavior of this multicationic pseudocapacitive material. Moreover, these in-depth experiments were obtained in real time upon cycling the electrode, which allowed investigating the reactions occurring in the material within a realistic timescale, which is compatible with electrochemical capacitors practical operation. Both Fe K-edge and W L 3-edge measurements point out the involvement of the Fe 3+ /Fe 2+ redox couple in the charge storage while W 6+ acts as a spectator cation. The result of this study enables to unambiguously discriminate between the Faradaic and capacitive behavior of FeWO 4. Beside these valuable insights toward the full description of the charge storage mechanism in FeWO 4 , this paper demonstrates the potential of operando X-ray absorption spectroscopy to enable a better material engineering for new high capacitance pseudocapacitive electrode materials.
Published: 2020
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21. Unveiling Pseudocapacitive Charge Storage Behavior in FeWO

Author: Nicolas, Goubard-Bretesché, Olivier, Crosnier, Camille, Douard, Antonella, Iadecola, Richard, Retoux, Christophe, Payen, Marie-Liesse, Doublet, Kazuaki, Kisu, Etsuro, Iwama, Katsuhiko, Naoi, Frédéric, Favier, and Thierry, Brousse
Abstract: In nanosized FeWO
Published: 2020

22. Unexpected band gap increase in the Fe2VAl Heusler compound

Author: Alexandre Berche, Philippe Jund, Marie-Liesse Doublet, Martin S. Talla Noutack, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)
Subjects: Materials science, Physics and Astronomy (miscellaneous), Band gap, FOS: Physical sciences, 02 engineering and technology, engineering.material, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Thermoelectric effect, Figure of merit, General Materials Science, thermally activated defects, Condensed Matter - Materials Science, Condensed matter physics, business.industry, thermoelectric materials, Materials Science (cond-mat.mtrl-sci), 021001 nanoscience & nanotechnology, Thermoelectric materials, Heusler compound, Semimetal, molecular dynamics, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Semiconductor, engineering, electronic properties, Density functional theory, Ab initio calculations, 0210 nano-technology, business, Heusler compounds, Energy (miscellaneous)
Abstract: Knowing the electronic structure of a material is essential in energy applications to rationalize its performance and propose alternatives. Materials for thermoelectric applications are generally small-gap semiconductors and should have a high figure of merit ZT. Even if the Fe2VAl Heusler compound has a decent ZT, its conductive nature (semi-metal or semiconductor) is not yet clarified especially at low temperature. In this paper, we focus our DFT calculations on the effect of temperature on the bandgap of Fe2VAl. In contrast to what is usually observed, we show that both the temperature increase and the formation of thermally-activated Al/V inversion defects (observed experimentally), open the bandgap. Such an unusual behavior is the key for reconciling all bandgap measurements performed on the Fe2VAl compound using a standard GGA functional and could be an efficient way for improving the thermoelectric properties of this family of materials., Comment: 10 pages, 5 figures
Published: 2020
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23. New p-type Al-substituted SrSnO

Author: Leila, Ben Amor, Besma, Belgacem, Jean-Sébastien, Filhol, Marie-Liesse, Doublet, Mouna, Ben Yahia, and Rached, Ben Hassen
Abstract: Novel p-type SrSn
Published: 2020

24. The Structural Stability of P2-Layered Na-Based Electrodes during Anionic Redox

Author: Marie-Liesse Doublet, Jean Vergnet, Matthieu Saubanère, Jean-Marie Tarascon, Collège de France (CDF), Collège de France (CdF), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), 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), 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), Chaire Chimie du solide et énergie, Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), 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), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)
Subjects: Materials science, Stacking, Disproportionation, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Redox, Cathode, 0104 chemical sciences, law.invention, Hysteresis, General Energy, law, Structural stability, Chemical physics, Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Density functional theory, 0210 nano-technology, [CHIM.OTHE]Chemical Sciences/Other, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; The need to store an ever increasing amount of renewable energy in a sustainable way has rekindled interest for Na-ion batteries owing to the abundance of Na. Their energy density, lower than Li-Ion, can be enhanced by unlocking anionic redox, as recently reported in Na-deficient P2-phases. In contrast to their Li-rich counterparts with O3 stacking, these Na-deficient P2-phases show surprisingly good structural stability during anionic redox. Understanding the fundamental science at work in the relation between O/P stacking and anionic redox reversibility is critical to design stable anionic redox cathodes. Herein, through DFT-based analysis of the model compounds O2-and P2-Na2∕ 3Mg1∕3Mn2∕3O2, we show that the anionic redox process corresponds to a highly reversible collective distortion of the oxygen network in P stacking, or to a disproportionation of the oxygen pairs associated with significant voltage hysteresis in O stacking. Based on these findings, we used a magnetic-constrained DFT methodology to quantitatively predict the composition range of the reversible cycling that we successfully extend to other Mn-based cathodes (Na2∕ 3Zn1∕3Mn2∕3O2, Na 2 Mn 3 O 7). This article thus provides fundamental understanding, powerful computational methods and practical guidelines to design more stable anionic redox compounds.
Published: 2020
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25. Electrolyte Reactivity in the Double Layer in Mg Batteries: An Interface Potential-Dependent DFT Study

Author: Jean-Sébastien Filhol, T. Rejec, Robert Dominko, Marie-Liesse Doublet, Jan Bitenc, Anja Kopač Lautar, Laboratory for Materials Electrochemistry, National Institute of Chemistry, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), University of Ljubljana, Jozef Stefan Institute [Ljubljana] (IJS), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-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), 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), 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 ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)
Subjects: Double layer (biology), Battery (electricity), Chemical substance, General Chemistry, Electrolyte, 010402 general chemistry, Electrochemistry, 01 natural sciences, Biochemistry, Catalysis, Dimethoxyethane, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry.chemical_compound, Colloid and Surface Chemistry, chemistry, Chemical engineering, [CHIM]Chemical Sciences, Chemical stability, [CHIM.OTHE]Chemical Sciences/Other, Ethylene carbonate, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; The electrochemical degradation of two solvent-based electrolytes for Mg-metal batteries is investigated through a Grand canonical DFT approach. Both electrolytes are highly reactive in the double layer region where the solvated species have no direct contact with the Mg-surface, hence emphasising that surface reactions are not the only phenomena responsible for electrolyte degradation. Applied to dimethoxyethane (DME) and ethylene carbonate (EC), the present methodology shows that both solvents should thermodynamically decompose in the double layer prior to the Mg 2+ /Mg 0 reduction, leading to electrochemically inactive reaction products. Based on thermodynamic considerations, Mg 0 deposition should not be possible, which is not in agreement with experiments, at least for DME-based electrolytes. This apparent contradiction is here addressed through the rationalization of the electrochemical mechanism underlying solvent electro-activation. An extended operation potential window (OPW) is defined, in which the Mg 2+ /Mg 0 reduction can compete with electrolyte decomposition, thus enabling battery operation beyond the solvated species thermodynamic stability. The chemical study of the degradation products is in excellent agreement with experiments and it offer rationale for the Mg-battery failure in EC electrolyte and 2 capacity fade in DME electrolyte. Potential-dependent approach proposed herein is thus able to successfully tackle the challenging problem of interface electrochemistry. Being fully transferable to any other electrochemical systems, this methodology should provide rational guidelines for the development of viable electrolytes for multivalent batteries, and more generally, energy conversion and storage devices.
Published: 2020
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26. Thermodynamic origin of dendrite growth in metal anode batteries

Author: Marie-Liesse Doublet, Arthur Hagopian, Jean-Sébastien Filhol, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), and Centre National de la Recherche Scientifique (CNRS)
Subjects: Battery (electricity), Materials science, Renewable Energy, Sustainability and the Environment, 02 engineering and technology, Electrolyte, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Pollution, Capacitance, 0104 chemical sciences, Metal, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Dendrite (crystal), Nuclear Energy and Engineering, Chemical physics, Whisker, visual_art, Electrode, visual_art.visual_art_medium, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Environmental Chemistry, 0210 nano-technology, Short circuit, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; The formation of dendrites in alkali and alkaline earth-metal batteries leads to short circuit and catastrophic battery failure which hinders the development of high-energy-density battery technology. Herein, we investigate the thermodynamic origin of this complex phenomenon and show that kinetic transport limitation of metal cations in the electrolyte is not the only factor controlling the formation of dendrites. The specific behavior of Li, Na and Mg electrodes towards dendritic growth is straightforwardly deduced from the shape of their electro-capillary diagrams, as computed from a grand canonical DFT approach. The whisker and dendrite morphologies associated with the different growth regimes are fully rationalized by the present methodology and the critical parameters controlling the dendritic growth on metallic surfaces are clearly identified. Further improving the description of the interface by means of a simplified yet realistic SEI built on carbonate-based decomposition products, we show that the over-potentials at which each growth regime is expected to occur can be predicted at a quantitative level, hence allowing the design of chemical strategies to prevent dendrite growth at metallic surfaces. More specifically, high surface tension associated with low surface capacitance and low potential of zero-charge is the target triptych to favor safe battery operation and can be obtained through appropriate chemical engineering.
Published: 2020
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27. Atomic Structure of 2 nm Size Metallic Cobalt Prepared by Electrochemical Conversion: An in Situ Pair Distribution Function Study

Author: Damien Dambournet, Wei Li, Peter J. Chupas, Karena W. Chapman, Matthieu Saubanère, Marie-Liesse Doublet, Delphine Flahaut, Olaf J. Borkiewicz, PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), X-ray Science Division (XSD), 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), 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), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Argonne National Laboratory [Lemont] (ANL), 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), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)
Subjects: Diffraction, Atoms, Materials science, chemistry.chemical_element, Nanoparticle, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Metal, Physical and Theoretical Chemistry, Pair distribution function, Cobalt, Particle size, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, General Energy, chemistry, Chemical engineering, visual_art, Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], visual_art.visual_art_medium, 0210 nano-technology
Abstract: International audience; Conversion reactions, offering high capacity in batteries, imply a restructuration of the pristine atomic structure down to the nanoscale. The associated large broadening in the Bragg peaks of the restructured electrode renders the description of atomic structure, almost impossible using conventional X-ray diffraction. On the other hand, atomic pair distribution function (PDF) is well suited to probe the structure of few nanometer-sized particles. Here, we investigated the formation mechanism and structure of 2 nm particle size of metallic Co obtained by electrochemical conversion of CoF2. We found that the conversion process stabilized a disordered structure consisting of a hexagonal-close-pack-face-centered-pack intergrowth. The reaction was followed by in situ PDF, providing unique insight into the growth of highly defective Co nanoparticles.
Published: 2018
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28. (Invited) The Challenge of High Energy Density in Li/Na-Ion Batteries

Author: Marie-Liesse Doublet
Subjects: Materials science, Energy density, Analytical chemistry
Published: 2021
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29. Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries

Author: Ying Xie, Matthieu Saubanère, Marie-Liesse Doublet, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, 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), 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), 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 ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)
Subjects: Renewable Energy, Sustainability and the Environment, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Pollution, Oxygen, Redox, Reductive elimination, 0104 chemical sciences, Ion, Nuclear Energy and Engineering, chemistry, Chemical physics, Structural stability, Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Environmental Chemistry, Electron configuration, 0210 nano-technology
Abstract: International audience; The structural stability and the redox mechanism of Li-rich layered oxides (LLOs) are two very important aspectsfor high energy density. The former is related to the irreversible loss of lattice oxygen and capacity fading duringcycling, while the latter determines the overall capacity of the materials. This paper aims at clarifying the factorsgoverning the structural stability, the extra capacity and the redox mechanism of LLOs upon Li-removal. Theresults show that the structural stability against oxygen vacancy formation is improved with increasing M–Ocovalency, while it decreases with increasing d-shell electron number and with electrochemical extraction oflithium from the lattice. The redox mechanism of Li2-xMO 3 electrodes formed by 3d metals or by heavier metals0with a d electronic configuration is related to the electron depletion from the oxygen lone-pairs (localized non-bonding O(2p) states) leading to an irreversible anionic redox ending with the reductive elimination of O 2 uponcycling. For these phases, long-term cycling is predicted to be very unlikely due to the irreversible loss of latticenoxygen upon charging. For the electrodes formed by 4d and 5d metals with intermediate d electronicconfigurations, reversible cationic and anionic redox activities are predicted, therefore enabling reversible extra-capacities. The very different redox mechanisms exhibited by Li2-x MO3 electrodes are then linked to the delicatebalance between the Coulomb repulsions (U term) and the M–O bond covalency (D term) through the generaldescription of charge-transfer vs. Mott–Hubbard insulators. The present findings will provide a uniformguideline for tuning the band structures of Li2MO 3 phases and thus activating desired redox mechanisms,being beneficial for the design of high-energy density electrode materials for Li-ion battery applications
Published: 2017
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30. Unveiling Pseudocapacitive Charge Storage Behavior in FeWO4 Electrode Material by Operando X-ray Absorption Spectroscopy

Author: Nicolas Goubard-Bretesché, Olivier Crosnier, Camille Douard, Antonella Iadecola, Richard Retoux, Christophe Payen, Marie-Liesse Doublet, Kazuaki Kisu, Etsuro Iwama, Katsuhiko Naoi, Frédéric Favier, and Thierry Brousse
Abstract: In nano-sized FeWO4 electrode material, both Fe and W metal cations are suspected to be involved in the fast and reversible Faradaic surface reactions giving rise to its pseudocapacitive signature. As for any other pseudocapacitive materials, to fully understand the charge storage mechanism, a deeper insight into the involvement of the electroactive cations still has to be provided. The present paper illustrates how operando X-ray absorption spectroscopy (XAS) has been successfully used to collect data of unprecedented quality allowing to elucidate the complex electrochemical behavior of this multicationic pseudocapacitive material. Moreover, these in-depth experiments were obtained in real time upon cycling the electrode, which allowed investigating the reactions occurring in the material within a realistic timescale, which is compatible with electrochemical capacitors practical operation. Both Fe K-edge and W L3-edge measurements point out the involvement of the Fe3+/Fe2+ redox couple in the charge storage while W6+ acts as a spectator cation. The result of this study enables to unambiguously discriminate between the Faradaic and capacitive behavior of FeWO4. Beside these valuable insights toward the full description of the charge storage mechanism in FeWO4, this paper demonstrates the potential of operando X-ray absorption spectroscopy to enable a better material engineering for new high capacitance pseudocapacitive electrode materials.
Published: 2019
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31. Unified picture of anionic redox in Li/Na-ion batteries

Author: Matthieu Saubanère, Marie-Liesse Doublet, Mouna Ben Yahia, Jean Vergnet, 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), 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), École des Ponts ParisTech (ENPC), Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), 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), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), and Collège de France (CdF)
Subjects: Materials science, Mechanical Engineering, Cationic polymerization, chemistry.chemical_element, Charge (physics), 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, Oxygen, Redox, Electron localization function, 0104 chemical sciences, chemistry, Transition metal, Mechanics of Materials, Chemical physics, Electrode, [CHIM]Chemical Sciences, General Materials Science, 0210 nano-technology, Lone pair
Abstract: International audience; Anionic redox in Li-rich and Na-rich transition metal oxides (A-rich-TMOs) has emerged as a new paradigm to increase the energy density of rechargeable batteries. Ever since, numerous electrodes delivering extra anionic capacity beyond the theoretical cationic capacity have been reported. Unfortunately, most often the anionic capacity achieved in charge is partly irreversible in discharge. A unified picture of anionic redox in A-rich-TMOs is designed here to identify the electronic origin of this irreversibility and to propose new directions to improve the cycling performance of the electrodes. The electron localization function is introduced as a holistic tool to unambiguously locate the oxygen lone pairs in the structure and follow their participation in the redox activity of A-rich-TMOs. The charge-transfer gap of transition metal oxides is proposed as the pertinent observable to quantify the amount of extra capacity achievable in charge and its reversibility in discharge, irrespective of the material chemical composition. From this generalized approach, we conclude that the reversibility of the anionic capacity is limited to a critical number of O holes per oxygen, hO ≤ 1/3.
Published: 2019
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32. Zn 0.35 Co 0.65 O – A Stable and Highly Active Oxygen Evolution Catalyst Formed by Zinc Leaching and Tetrahedral Coordinated Cobalt in Wurtzite Structure

Author: Norbert Koch, Sayed M. El-Refaei, Ana Guilherme Buzanich, Sebastian Wahl, Marie-Liesse Doublet, Kug-Seung Lee, Nicola Pinna, Patrick Amsalem, Humboldt-Universität zu Berlin, BAM Bundesanstalt für Materialforschung u. -prüfung, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-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), Humboldt University Of Berlin, 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), 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 ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)
Subjects: Materials science, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, Zinc, Overpotential, 010402 general chemistry, Electrochemistry, 01 natural sciences, 7. Clean energy, Catalysis, Structure-Property Relationships, General Materials Science, γ-Co(O)OH, Wurtzite crystal structure, Renewable Energy, Sustainability and the Environment, zinc, Oxygen evolution, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, cobalt, 0104 chemical sciences, chemistry, oxygen evolution reaction, Leaching (metallurgy), 0210 nano-technology, Cobalt, Wurtzite
Abstract: International audience; To arrive to sustainable hydrogen-based energy solutions, the understanding of water-splitting catalysts plays the most crucial role. Herein, we combined state-of-the-art hypotheses on electrocatalytic active metal sites towards the oxygen evolution reaction (OER) to develop a highly efficient catalyst based on earth-abundant cobalt and zinc oxides. The precursor catalyst Zn 0.35 Co 0.65 O was synthesized via a fast microwave-assisted approach at low temperatures. Subsequent, it transformed in situ from the Wurtzite structure to the layered γ-Co(O)OH, while most of its zinc leaches out. This material shows outstanding catalytic performance and stability towards the OER in 1 M KOH (overpotential at 10 mA cm-2 η initial = 306 mV, η 98 h = 318 mV). By comparing the electrochemical results and ex situ analyses to today's literature, we were able to identify clear structure-activity correlations. Our findings suggest that coordinately unsaturated cobalt octahedra on the surface are indeed the active centers for the OER.
Published: 2019
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33. Evolution of Oxygen Ligands upon Large Redox Swings of Li3IrO4

Author: Jordi Cabana, Jean-Marie Tarascon, Marie-Liesse Doublet, Teak D. Boyko, Arnaud J. Perez, John W. Freeland, Beata Taudul, Haifeng Li, 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), 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), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry, University of Illinois at Chicago, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Argonne National Laboratory [Lemont] (ANL), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Chaire Chimie du solide et énergie, University of Illinois [Chicago] (UIC), and University of Illinois System
Subjects: Materials science, Renewable Energy, Sustainability and the Environment, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Photochemistry, 01 natural sciences, Redox, Oxygen, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Materials Chemistry, Electrochemistry, [CHIM]Chemical Sciences, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: International audience; The limits of intercalation electrochemistry continue to be tested in the quest for ever increasing gains in the storage capability of Li-ion cathodes. The subsequent push for multi-electron reactivity has led to the recognition of the extremely versatile role of oxide ligands in charge compensation when there is a large redox swing. Li 3 IrO 4 is a unique model of such activity because it can reversibly cycle between Li 1 IrO 4 and Li 4.7 IrO 4. Here, X-ray spectroscopy, magnetic measurements and computational simulations uncover the evolution of O states in the different steps, compared to the involvement of Ir. While the process between Li 1 IrO 4 and Li 3 IrO 4 is dominated by the unconventional lattice oxygen redox, the process between Li 3 IrO 4 and Li 4.7 IrO 4 involves a conventional change of the formal oxidation state of Ir, which affects O due to the high covalency. The O states of Li 3 IrO 4 exhibit a very high reversibility after the whole 3.7-electron process, completely restoring the pristine state.
Published: 2021
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34. Elucidation of Active Oxygen Sites upon Delithiation of Li3IrO4

Author: Haifeng Li, Marie-Liesse Doublet, Jordi Cabana, Jean-Marie Tarascon, Arnaud J. Perez, Teak D. Boyko, John W. Freeland, Beata Taudul, Department of Chemistry, University of Liverpool, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Argonne National Laboratory [Lemont] (ANL), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), University of Illinois [Chicago] (UIC), and University of Illinois System
Subjects: Battery (electricity), Renewable Energy, Sustainability and the Environment, Chemistry, Inorganic chemistry, Oxide, Energy Engineering and Power Technology, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Cathode, 0104 chemical sciences, Redox Activity, law.invention, Active oxygen, chemistry.chemical_compound, Fuel Technology, Transition metal, Chemistry (miscellaneous), law, Materials Chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: Transformational increases in the storage capacity of battery cathodes could be achieved by tapping into the redox activity at oxide ligands in addition to conventional transition metal couples. Yet the key signatures that govern such lattice oxygen redox (LOR) have not been ascertained. Li3IrO4 has the largest reversible LOR, rendering it a unique model system. Here, X-ray spectroscopy and computational simulations reveal that LOR in Li3IrO4 is selectively compensated via O sites with 3 lone pairs, which are activated by Li/Ir disorder. The 2-electron LOR can be reversed to regenerate the initial state without unlocking competing bulk reactions observed in many other compounds. We uncover an intricate interplay between stoichiometry, O coordination and non-bonding states in LOR and pinpoint spectroscopic signatures. This interplay is indispensable to design materials with 3d metals that fulfill the promise of LOR to overcome the bottlenecks of current cathodes for future implementation in practical batteries.
Published: 2021
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35. Chemical Activity of the Peroxide/Oxide Redox Couple: Case Study of Ba 5 Ru 2 O 11 in Aqueous and Organic Solvents

Author: Alexis Grimaud, John W. Freeland, Jean-Marie Tarascon, Antonella Iadecola, Haifeng Li, Matthieu Saubanère, Dmitry Batuk, Marie-Liesse Doublet, Jordi Cabana, Gwenaëlle Rousse, Artem M. Abakumov, Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-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), Electron Microscopy for Materials Science - EMAT (Antwerp, Belgium), Universiteit Antwerpen = University of Antwerpen [Antwerpen], 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), Argonne National Laboratory [Lemont] (ANL), University of Illinois [Chicago] (UIC), University of Illinois System, Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chaire Chimie du solide et énergie, 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), Universiteit Antwerpen [Antwerpen], Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)
Subjects: General Chemical Engineering, Oxide, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Photochemistry, Electrocatalyst, Electrochemistry, 01 natural sciences, 7. Clean energy, Peroxide, Redox, Oxygen, Article, chemistry.chemical_compound, Materials Chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, Aqueous solution, Physics, Oxygen evolution, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Chemistry, chemistry, 13. Climate action, 0210 nano-technology
Abstract: The finding that triggering the redox activity of oxygen ions within the lattice of transition metal oxides can boost the performances of materials used in energy storage and conversion devices such as Li-ion batteries or oxygen evolution electrocatalysts has recently spurred intensive and innovative research in the field of energy. While experimental and theoretical efforts have been critical in understanding the role of oxygen nonbonding states in the redox activity of oxygen ions, a clear picture of the redox chemistry of the oxygen species formed upon this oxidation process is still missing. This can be, in part, explained by the complexity in stabilizing and studying these species once electrochemically formed. In this work, we alleviate this difficulty by studying the phase Ba5Ru2O11, which contains peroxide O-2(2-) groups, as oxygen evolution reaction electrocatalyst and Li-ion battery material. Combining physical characterization and electrochemical measurements, we demonstrate that peroxide groups can easily be oxidized at relatively low potential, leading to the formation of gaseous dioxygen and to the instability of the oxide. Furthermore, we demonstrate that, owing to the stabilization at high energy of peroxide, the high-lying energy of the empty sigma* antibonding O-O states limits the reversibility of the electrochemical reactions when the O-2(2-)/O2- redox couple is used as redox center for Li-ion battery materials or as OER redox active sites. Overall, this work suggests that the formation of true peroxide O-2(2-) states are detrimental for transition metal oxides used as OER catalysts and Li-ion battery materials. Rather, oxygen species with O-O bond order lower than 1 would be preferred for these applications.
Published: 2018
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36. The Electrochemical Sodiation of Sb Investigated by Operando X-ray Absorption and 121Sb Mössbauer Spectroscopy: What Does One Really Learn?

Author: Moulay Tahar Sougrati, Laure Monconduit, Raphaël P. Hermann, Marie-Liesse Doublet, Abdelfattah Mahmoud, Lorenzo Stievano, Bernard Fraisse, Mouna Ben Yahia, Ali Darwiche, Marcus Fehse, Camille La Fontaine, 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), European Synchroton Radiation Facility [Grenoble] (ESRF), Delft University of Technology (TU Delft), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Group of Research in Energy and ENvironment from MATerials (GREENMAT), Université de Liège, Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Oak Ridge National Laboratory [Oak Ridge] (ORNL), UT-Battelle, LLC, 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), European Project: 28721,ALISTORE, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Dutch Belgian Beam line (DUBBLE), European Synchrotron Radiation Facility (ESRF), 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), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)
Subjects: Materials science, Absorption spectroscopy, Analytical chemistry, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, DFT calculations, 01 natural sciences, Na-ion batteries, Antimony, Ab initio quantum chemistry methods, Phase (matter), Mössbauer spectroscopy, lcsh:TK1001-1841, Electrochemistry, Electrical and Electronic Engineering, Absorption (electromagnetic radiation), X-ray absorption spectroscopy, [CHIM.MATE]Chemical Sciences/Material chemistry, alloy reaction, 021001 nanoscience & nanotechnology, chemometrics, 3. Good health, 0104 chemical sciences, Amorphous solid, lcsh:Production of electric energy or power. Powerplants. Central stations, MCR-ALS, chemistry, lcsh:Industrial electrochemistry, 0210 nano-technology, Sb, lcsh:TP250-261
Abstract: In this study, we want to highlight the assets and restrictions of X-ray absorption spectroscopy (XAS) and M&ouml, ssbauer spectroscopy for investigating the mechanism of the electrochemical reaction of antimony electrode materials vs. Na. For this, operando XAS was carried out during the first one and a half cycles, and the whole set of measured data was analysed using a statistical-chemometric approach, while low temperature M&ouml, ssbauer spectroscopy measurements were carried out ex situ on selected samples stopped at different points of the electrochemical reaction. Complementary ab initio calculations were performed to support the experimental findings. Both techniques show that, upon the first sodiation, most Sb reacts with Na to form disordered Na 3 Sb. This step is accompanied by the formation of amorphous Sb as an intermediate. Upon inversion of the current Na 3 Sb is desodiated and an amorphous Sb phase, distinct from the pristine bulk Sb state, is gradually formed. However, both XAS and M&ouml, ssbauer spectroscopy were unable to spot the formation of intermediate Na x Sb phases, which were evinced in previous works by operando Pair Distribution Function analyses. The results shown here clearly assign such failure to the intrinsic inability of both techniques to identify these intermediates.
Published: 2018
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37. A chemical approach to raise cell voltage and suppress phase transition in O3 sodium layered oxide electrodes

Author: Jean-Marie Tarascon, Joke Hadermann, Quentin Jacquet, Mariyappan Sathiya, Olesia M. Karakulina, Marie-Liesse Doublet, Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), 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), Sorbonne Université (SU), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Electron Microscopy for Materials Science - EMAT (Antwerp, Belgium), Universiteit Antwerpen [Antwerpen], Collège de France - Chaire Chimie du solide et énergie, 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), 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), and Universiteit Antwerpen = University of Antwerpen [Antwerpen]
Subjects: Phase transition, Materials science, Oxide, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 7. Clean energy, 01 natural sciences, Redox, Metal, chemistry.chemical_compound, Transition metal, Phase (matter), [CHIM]Chemical Sciences, General Materials Science, Renewable Energy, Sustainability and the Environment, Physics, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Chemistry, Chemical engineering, chemistry, visual_art, Electrode, visual_art.visual_art_medium, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, Engineering sciences. Technology
Abstract: International audience; Sodium ion batteries (NIBs) are one of the versatile technologies for low‐cost rechargeable batteries. O3‐type layered sodium transition metal oxides (NaMO2, M = transition metal ions) are one of the most promising positive electrode materials considering their capacity. However, the use of O3 phases is limited due to their low redox voltage and associated multiple phase transitions which are detrimental for long cycling. Herein, a simple strategy is proposed to successfully combat these issues. It consists of the introduction of a larger, nontransition metal ion Sn4+ in NaMO2 to prepare a series of NaNi0.5Mn0.5− y Sn y O2 (y = 0–0.5) compositions with attractive electrochemical performances, namely for y = 0.5, which shows a single‐phase transition from O3 ⇔ P3 at the very end of the oxidation process. Na‐ion NaNi0.5Sn0.5O2/C coin cells are shown to deliver an average cell voltage of 3.1 V with an excellent capacity retention as compared to an average stepwise voltage of ≈2.8 V and limited capacity retention for the pure NaNi0.5Mn0.5O2 phase. This study potentially shows the way to manipulate the O3 NaMO2 for facilitating their practical use in NIBs.
Published: 2018
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38. Competition between Metal Dissolution and Gas Release in Li-Rich Li 3 Ru y Ir 1– y O 4 Model Compounds Showing Anionic Redox

Author: Quentin Jacquet, Gwenaëlle Rousse, Matthieu Saubanère, Antonella Iadecola, Jean-Marie Tarascon, Erik J. Berg, Marie-Liesse Doublet, Daniel Alves Dalla Corte, Louis Lemarquis, Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-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), 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), Paul Scherrer Institute (PSI), Chaire Chimie du solide et énergie, 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), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)
Subjects: Materials science, Absorption spectroscopy, 020209 energy, General Chemical Engineering, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, Mass spectrometry, Redox, Ultraviolet visible spectroscopy, Chemical engineering, 0202 electrical engineering, electronic engineering, information engineering, Materials Chemistry, Degradation (geology), [CHIM]Chemical Sciences, Density functional theory, 0210 nano-technology, Dissolution
Abstract: The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.8b02955. Crystallographic data, additional Rietveld refinements, and EXAFS analysis (PDF) PDF cm8b02955_si_001.pdf (1.91 MB); International audience; Li-ion batteries have experienced tremendous progress over the past decade; however, their energy density should still be increased to power electric vehicles. Following this aim, the energy density of the cathode material can be drastically increased by making use of anionic redox, although it often comes along with material degradation. In this study, through a detailed analysis of the charge compensation mechanism of Li3RuO4 by online electrochemical mass spectrometry, X-ray absorption spectroscopy, and ultraviolet spectroscopy, we unveiled a new degradation mechanism for a cathode material showing anionic redox, namely the dissolution of Ru forming RuO4/RuO4– species with limited release of gas from the material. We show that this dissolution can be effectively tackled by substituting Ru with Ir. However, such a strategy leads to a massive increase in the release of O2 gas at the end of the charge. Density functional theory calculations prove that the relative stability of the end members RuO4 and IrO4 versus oxygen release is at the origin of this competition between metal dissolution and gas release.
Published: 2018
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39. Electrochemical Mg alloying properties along the Sb1-xBix solid solution

Author: Danielle Laurencin, Fabrizio Murgia, Marie-Liesse Doublet, Romain Berthelot, Ephrem Terefe Weldekidan, Lorenzo Stievano, Laure Monconduit, 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), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), PEPS CNRS 2014 Alabama and 2015 SurfMag, ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010), 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), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and 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)
Subjects: Diffraction, Materials science, General Chemical Engineering, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 25Mg solid-state NMR, DFT calculations, 01 natural sciences, Bismuth, Ball milling, Antimony, [CHIM]Chemical Sciences, Nuclear magnetic resonance spectroscopy, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Operando XRD, 0104 chemical sciences, Mg-battery, chemistry, Electrode, Density functional theory, 0210 nano-technology, Solid solution
Abstract: International audience; Despite strong physical and chemical similarities between antimony and bismuth, a distinct behaviour is observed in the electrochemical magnesiation of their micrometric powders. Bismuth undergoes a complete and highly reversible alloying reaction, whereas antimony displays no electrochemical activity. Taking advantage of the complete SbBi solid solution, monophasic compositions Sb1-xBix were prepared by high-energy mechanochemical synthesis and characterized by X-ray diffraction and solid-state 25Mg nuclear magnetic resonance spectroscopy. The electrochemical magnesiation at low current rate shows a full alloying process of Sb1-xBix-based electrodes leading to monophasic Mg3(Sb1-xBix)2. This chemical association of antimony and bismuth enables a positive effect on the electrochemical magnesiation of the electrode and enables higher specific capacities compared to Bi-based electrodes. However, this synergy only operates in the nominal discharge since an irreversible capacity loss, which scales with the antimony content, is observed in the subsequent charge. Operando XRD reveals a complex segregation process leading to pure bismuth and Mg3Sb2 at the end of charge which is further rationalized by density functional theory calculations as an instability of the Mg3(Sb1-xBix)2 solid solution.
Published: 2018
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40. Electrostatic interactions vs. second order Jahn-Teller distortion as the source of structural diversity in Li 3 MO 4 compounds (M = Ru, Nb, Sb and Ta)

Author: Gwenaëlle Rousse, Quentin Jacquet, Matthieu Saubanère, Jean-Marie Tarascon, Marie-Liesse Doublet, Antonella Iadecola, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), 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), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Chaire Chimie du solide et énergie, Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie et de physique des milieux condensés (IMPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), 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), 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), 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), Collège de France - Chaire Chimie du solide et énergie, and Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)
Subjects: Diffraction, Materials science, Absorption spectroscopy, General Chemical Engineering, Jahn–Teller effect, Cationic polymerization, Structural diversity, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrostatics, 01 natural sciences, 0104 chemical sciences, Crystallography, Order (biology), Materials Chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, Superstructure (condensed matter), ComputingMilieux_MISCELLANEOUS
Abstract: International audience; With the advent of layered rocksalt oxides showing anionic redox activity toward Li, there has been an increased focus on designing new rocksalt structures and, more particularly, compounds pertaining to the Li3MO4 family. The structural richness of this family is nested in its ability to host many different cations, leading to the formation of superstructure patterns whose predictability is still limited. Thus, there is a need to understand the formation of such superstructures, as cationic arrangements have a crucial effect on their physical properties. Herein we propose a combined experimental and theoretical approach to understand the interactions governing cation ordering in binary systems of general composition given by Li3MyM′1–yO4 (M and M′ being Ru, Nb, Sb, and Ta). Through complementary X-ray diffraction and X-ray absorption spectroscopy techniques, we reveal a solid-solution behavior for the Li3RuySb1–yO4 system, as opposed to Li3SbyNb1–yO4 that enlists four rocksalt structures with different cation orderings. We use DFT calculations to rationalize such a structural diversity and find that it is controlled by a delicate balance between electrostatic interactions and charge transfer due to a second order Jahn–Teller distortion. This insight provides a new viewpoint for understanding cationic arrangements in rocksalt structures and guidelines to design novel phases for applications such as Li-ion batteries or ionic conductors.
Published: 2018
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41. Origin of the Voltage Hysteresis of MgH2 Electrodes in Lithium Batteries

Author: Marie-Liesse Doublet, Guido Gigli, Sergio Brutti, Daniele Meggiolaro, Priscilla Reale, Annalisa Paolone, and Reale, P.
Subjects: Lithium-ion batteries, Work (thermodynamics), Analytical chemistry, chemistry.chemical_element, Thermodynamics, surfaces, coatings and films, Condensed Matter::Materials Science, chemistry.chemical_compound, Elementary reaction, physical and theoretical chemistry, electronic, optical and magnetic materials, surfaces, coatings and films, energy, optical and magnetic materials, Physical and Theoretical Chemistry, electronic, Magnesium hydride, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Anode, Hysteresis, Energy efficiency, General Energy, chemistry, Lithium, Density functional theory, Voltage
Abstract: Magnesium hydride has been proposed as innovative anode material for Li ion cells due to its large theoretical capacity and high-energy efficiency compared to other conversion materials. In this work, we report a combined experimental-theoretical study about the origin of voltage hysteresis in the conversion reaction of MgH2 in lithium cells. Experimentally, the extent of the thermodynamic voltage hysteresis in the first galvanostatic discharge-charge cycle has been determined by the GITT technique and decoupled from the kinetic overpotentials. Theoretically, the origin of the thermodynamic voltage hysteresis has been evaluated and studied by means density functional theory calculations within the supercell approach. Different elementary reactions have been modeled upon reduction and oxidation on the surfaces of the active phases (i.e., MgH2, LiH, and Mg), and the associated theoretical voltages have been predicted. Experimental and theoretical results have been compared and discussed to draw a comprehensive description of the elementary surface reactions of the MgH2 conversion in lithium cells. © 2015 American Chemical Society.
Published: 2015
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42. The electrochemical activity of the nitrosyl ligand in copper nitroprusside: a new possible redox mechanism for lithium battery electrode materials?

Author: Moulay Tahar Sougrati, Marco Giorgetti, Marie-Liesse Doublet, Lorenzo Stievano, Angelo Mullaliu, Giuliana Aquilanti, Nicolas Louvain, Alma Mater Studiorum Università di Bologna [Bologna] (UNIBO), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-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), Chimie, Ingénierie Moléculaire et Matériaux d'Angers (CIMMA), Université d'Angers (UA)-Centre National de la Recherche Scientifique (CNRS), Elettra Sincrotrone Trieste, Mullaliu, A., Sougrati, M. -. T. b, Louvain, N. b, Aquilanti, G., Doublet, M. -. L., Stievano, L., Giorgetti, M., 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), 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 ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)
Subjects: Nitrosyl group, Chemistry, Ligand, General Chemical Engineering, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, Prussian blue analog, [CHIM.MATE]Chemical Sciences/Material chemistry, Operando characterization, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Redox, Copper, Lithium battery, 0104 chemical sciences, X-ray absorption fine structure, Lithium, Fourier transform infrared spectroscopy, 0210 nano-technology, Reduction mechanism
Abstract: International audience; The unconventional redox mechanism of copper nitroprusside in the electrochemical reaction with lithium is studied by a wide range of techniques. After a simple and reproducible synthesis, pristine copper nitroprusside is characterized using a wide range of techniques. The material is formulated and electrochemically tested in coin cells to explore its electrochemical signature and cyclability. Multiple redox processes involving both Fe and Cu centres are identified at an early stage and further investigated by operando XAFS. Moreover, operando FTIR unveils the unexpected participation of the nitrosyl ligand in the electrochemical reaction. A gradual and irreversible transformation of the material, also reported by operando Mössbauer spectroscopy, occurs in the first cycles. Then, the material is able to withstand several electrochemical cycles without efficiency loss, even though no optimization on formulation has been carried out. Altogether, the nitrosyl group is electrochemically active beyond metals’ centres, giving as result a remarkable increase in capacity compared to other analogue compounds. We thus believe this study may open the way to further research on other electroactive nitrosyl-containing materials.
Published: 2017
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43. Erratum: Activation of surface oxygen sites on an iridium-based model catalyst for the oxygen evolution reaction

Author: Alexis Grimaud, Arnaud Demortière, Matthieu Saubanère, Walid Dachraoui, Martial Duchamp, Marie-Liesse Doublet, and Jean-Marie Tarascon
Subjects: Fuel Technology, Renewable Energy, Sustainability and the Environment, Energy Engineering and Power Technology, Electronic, Optical and Magnetic Materials
Published: 2017
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44. Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3

Author: Artem M. Abakumov, Dominique Foix, Arnaud J. Perez, Gustaaf Van Tendeloo, Marie-Liesse Doublet, Paul E. Pearce, Jean-Marie Tarascon, Dmitry Batuk, Mathieu Saubanère, Gwenaëlle Rousse, Eric McCalla, Chimie du solide et de l'énergie (CSE), Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU), 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), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), University of Antwerp (UA), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Minnesota [Twin Cities] (UMN), University of Minnesota System, Skolkovo Institute of Science and Technology [Moscow] (Skoltech), Chaire Chimie du solide et énergie, Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-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), 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), Collège de France - Chaire Chimie du solide et énergie, Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC), and EMAT University of Antwerp - Groenenborgerlaan 171, B-2020 Antwerp, Belgique
Subjects: Solid-state chemistry, Inorganic chemistry, Neutron diffraction, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Redox, Solid state chemistry, Batteries, [CHIM]Chemical Sciences, General Materials Science, Batteries, Solid state chemistry, Chemistry, Physics, Mechanical Engineering, Cationic polymerization, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Crystallography, Mechanics of Materials, Transmission electron microscopy, Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Density functional theory, [CHIM.OTHE]Chemical Sciences/Other, 0210 nano-technology
Abstract: International audience; Lithium-ion battery cathode materials have relied on cationic redox reactions until the recent discovery of anionic redox activity in Li-rich layered compounds which enables capacities as high as 300 mAh g-1. In the quest for new high-capacity electrodes with anionic redox, a still unanswered question was remaining regarding the importance of the structural dimensionality. The present manuscript provides an answer. We herein report on a β-Li2IrO3 phase which, in spite of having the Ir arranged in a tridimensional (3D) framework instead of the typical two-dimensional (2D) layers seen in other Li-rich oxides, can reversibly exchange 2.5 e- per Ir, the highest value ever reported for any insertion reaction involving d-metals. We show that such a large activity results from joint reversible cationic (Mn+) and anionic (O2)n- redox processes, the latter being visualized via complementary transmission electron microscopy and neutron diffraction experiments, and confirmed by density functional theory calculations. Moreover, β-Li2IrO3 presents a good cycling behaviour while showing neither cationic migration nor shearing of atomic layers as seen in 2D-layered Li-rich materials. Remarkably, the anionic redox process occurs jointly with the oxidation of Ir4+ at potentials as low as 3.4 V versus Li+/Li0, as equivalently observed in the layered α-Li2IrO3 polymorph. Theoretical calculations elucidate the electrochemical similarities and differences of the 3D versus 2D polymorphs in terms of structural, electronic and mechanical descriptors. Our findings free the structural dimensionality constraint and broaden the possibilities in designing high-energy-density electrodes for the next generation of Li-ion batteries.
Published: 2017
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45. An Oxysulfate Fe2O(SO4)2 Electrode for Sustainable Li-Based Batteries

Author: Marie-Liesse Doublet, Moulay Tahar Sougrati, Artem M. Abakumov, Matthieu Courty, Gwenaëlle Rousse, Gustaaf Van Tendeloo, Meiling Sun, Jean-Marie Tarascon, 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), Université Pierre et Marie Curie - Paris 6 (UPMC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), 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), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Chaire Chimie du solide et énergie, and Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)
Subjects: Electrode material, Chemistry, Inorganic chemistry, Nanotechnology, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Biochemistry, Redox, Catalysis, 0104 chemical sciences, Colloid and Surface Chemistry, Octahedron, Phase (matter), Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology
Abstract: International audience; High-performing Fe-based electrodes for Li-based batteries are eagerly pursued because of the abundance and environmental benignity of iron, with especially great interest in polyanionic compounds because of their flexibility in tuning the Fe3+/Fe2+ redox potential. We report herein the synthesis and structure of a new Fe-based oxysulfate phase, Fe2O(SO4)2, made at low temperature from abundant elements, which electrochemically reacts with nearly 1.6 Li atoms at an average voltage of 3.0 V versus Li+/Li, leading to a sustained reversible capacity of ≈125 mAh/g. The Li insertion–deinsertion process, the first ever reported in any oxysulfate, entails complex phase transformations associated with the position of iron within the FeO6 octahedra. This finding opens a new path worth exploring in the quest for new positive electrode materials.
Published: 2014
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46. Author Correction: Unified picture of anionic redox in Li/Na-ion batteries

Author: Mouna Ben Yahia, Marie-Liesse Doublet, Matthieu Saubanère, and Jean Vergnet
Subjects: Mechanics of Materials, Chemistry, Mechanical Engineering, Published Erratum, Inorganic chemistry, General Materials Science, General Chemistry, Condensed Matter Physics, Redox
Published: 2019
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47. Modelling the Electrode/Electrolyte Interfaces

Author: Anja Kopač Lautar, Tomaž Rejec, Robert Dominko, Jean-Sébastien Filhol, and Marie-Liesse Doublet
Abstract: Electrochemical reactions are mainly governed by the interface properties and changing electrode potential. Understanding the nature of electrochemical electrode/electrolyte interfaces is thus a crucial step in the optimization of systems for energy conversion and storage. However, a generally accepted method to consider varying electrode potentials in first-principles calculations does not exist, and modelling interfaces remains one of the biggest challenges for the density functional theory (DFT) community. Implicit solvent model implemented in some DFT codes [1, 2] together with the inclusion of explicit solvent molecules was used on lithium system and the obtained results were in agreement with experimental values [3]. We use the same methodological approach to study Mg2+ solvated in monoglyme (DME) and in ethylene carbonate (EC). Using molecular DFT (Gaussian) we first determine the explicit first solvation shell of Mg2+ in DME and EC. The solvated Mg2+ complex is then placed in front of Mg electrode in the plane wave DFT calculations (VASP). Potential dependent grand canonical energies, equilibrium (redox) potentials and differential capacitance are obtained for both systems and are in excellent agreement with experimental results. We further develop the method to probe stability regions of the solvents at the interface. We find that the stability of the solvent molecules is drastically modified in the presence of Mg2+ . Furthermore, the presented methodological approach can be used to study decomposition pathways. The obtained results give valuable insights into why some solvents are not appropriate for Mg battery systems, and how electrolyte performance can be improved. [1] K. Mathew et al., The Journal of chemical physics 140, 084106 (2014). [2] K. Letchworth-Weaver et al., Physical Review B 86, 075140 (2012). [3] N. Lespes et al., Journal of chemical theory and computation 11, 33753382 (2015). [4] C. D. Taylor et al., Physical Review B 73, 165402 (2006).
Published: 2019
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48. Physical Multiscale Modeling and Numerical Simulation of Electrochemical Devices for Energy Conversion and Storage : From Theory to Engineering to Practice

Author: Alejandro A. Franco, Marie Liesse Doublet, Wolfgang G. Bessler, Alejandro A. Franco, Marie Liesse Doublet, and Wolfgang G. Bessler
Subjects: Electrochemistry, Industrial, Energy conversion
Abstract: The aim of this book is to review innovative physical multiscale modeling methods which numerically simulate the structure and properties of electrochemical devices for energy storage and conversion. Written by world-class experts in the field, it revisits concepts, methodologies and approaches connecting ab initio with micro-, meso- and macro-scale modeling of components and cells. It also discusses the major scientific challenges of this field, such as that of lithium-ion batteries. This book demonstrates how fuel cells and batteries can be brought together to take advantage of well-established multi-scale physical modeling methodologies to advance research in this area. This book also highlights promising capabilities of such approaches for inexpensive virtual experimentation.In recent years, electrochemical systems such as polymer electrolyte membrane fuel cells, solid oxide fuel cells, water electrolyzers, lithium-ion batteries and supercapacitors have attracted much attention due to their potential for clean energy conversion and as storage devices. This has resulted in tremendous technological progress, such as the development of new electrolytes and new engineering designs of electrode structures. However, these technologies do not yet possess all the necessary characteristics, especially in terms of cost and durability, to compete within the most attractive markets. Physical multiscale modeling approaches bridge the gap between materials'atomistic and structural properties and the macroscopic behavior of a device. They play a crucial role in optimizing the materials and operation in real-life conditions, thereby enabling enhanced cell performance and durability at a reduced cost. This book provides a valuable resource for researchers, engineers and students interested in physical modelling, numerical simulation, electrochemistry and theoretical chemistry.
Published: 2016

49. ChemInform Abstract: A2VO(SO4)2(A: Li, Na) as Electrodes for Li-Ion and Na-Ion Batteries

Author: Gwenaëlle Rousse, Daniel Alves Dalla Corte, Matthieu Saubanère, Marie-Liesse Doublet, Jean-Marie Tarascon, and Meiling Sun
Subjects: Crystallography, Chemistry, Phase (matter), Electrode, Vanadium, chemistry.chemical_element, Density functional theory, General Medicine, Crystal structure, Alkali metal, Electrochemistry, Ion
Abstract: We herein report the synthesis, crystal structure, and electrochemical performances of a new Li-based vanadium oxysulfate phase, Li2VO(SO4)2, whose structure is built on vanadyl-containing VO5 square-based pyramids and SO4 groups linked by vertices to form layers. Li2VO(SO4)2 presents a redox activity at 4.7 V vs Li+/Li0 with a reversible capacity of 50 mA·h/g, while the chemically similar but structurally different Na2VO(SO4)2 delivers a capacity of 60 mA h/g at 4.5 V vs Na+/Na0. Density functional theory calculations are also performed to rationalize our findings in terms of redox activity and phase stability.
Published: 2016
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50. Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li

Author: Paul E, Pearce, Arnaud J, Perez, Gwenaelle, Rousse, Mathieu, Saubanère, Dmitry, Batuk, Dominique, Foix, Eric, McCalla, Artem M, Abakumov, Gustaaf, Van Tendeloo, Marie-Liesse, Doublet, and Jean-Marie, Tarascon
Abstract: Lithium-ion battery cathode materials have relied on cationic redox reactions until the recent discovery of anionic redox activity in Li-rich layered compounds which enables capacities as high as 300 mAh g
Published: 2016

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