Author: "Marie-Liesse Doublet" - Searchworks@Jio Institute Digital Library Search Results

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170 results on '"Marie-Liesse Doublet"'

51. A2VO(SO4)2 (A = Li, Na) as Electrodes for Li-Ion and Na-Ion Batteries

Author: Gwenaëlle Rousse, Jean-Marie Tarascon, Marie-Liesse Doublet, Matthieu Saubanère, Daniel Alves Dalla Corte, Meiling Sun, 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), 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), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de recherche pour le développement [IRD] : UR206-Muséum national d'Histoire naturelle (MNHN)-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 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, 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), Muséum national d'Histoire naturelle (MNHN)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de recherche pour le développement [IRD] : UR206-Centre National de la Recherche Scientifique (CNRS), 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: Phase stability, General Chemical Engineering, Vanadium, chemistry.chemical_element, Nanotechnology, 02 engineering and technology, General Chemistry, Crystal structure, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, 0104 chemical sciences, Ion, Crystallography, chemistry, Phase (matter), Electrode, Materials Chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Density functional theory, 0210 nano-technology
Abstract: International audience; 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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52. ChemInform Abstract: A Fully Ordered Triplite, LiCuSO4F

Author: Matthieu Saubanère, Jean-Marie Tarascon, Daniel Alves Dalla Corte, Marie-Liesse Doublet, Meiling Sun, and Gwenaëlle Rousse
Subjects: Chemical engineering, Chemistry, Annealing (metallurgy), Anhydrous, General Medicine, Ball mill, Stoichiometry
Abstract: The title compound is prepared by ball milling and annealing of a stoichiometric mixture of anhydrous LiF and CuSO4 (Al2O3 boat, 400—415 °C, 8 h).
Published: 2016
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53. The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries

Author: Marie-Liesse Doublet, Jean-Marie Tarascon, Eric McCalla, Matthieu Saubanère, 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), 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), 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 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, 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), 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: Battery (electricity), Renewable Energy, Sustainability and the Environment, Chemistry, Inorganic chemistry, Cationic polymerization, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Pollution, Redox, Cathode, Energy storage, 0104 chemical sciences, law.invention, Ion, Nuclear Energy and Engineering, Transition metal, law, Chemical physics, Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Environmental Chemistry, 0210 nano-technology
Abstract: The energy density delivered by a Li-ion battery is a key parameter that needs to be significantly increased to address the global question of energy storage for the next 40 years. This quantity is difficult to improve when materials exhibit a classical cationic redox activity. Recently, a cumulative cationic (M4+/M5+) and anionic (2O2-/(O2)n-) redox activity has been demonstrated in the Li-rich Li2MO3 family of compounds, therefore enabling doubling the energy density with respect to high-potential cathodes such as transition metal phosphates and sulfates. This paper aims at clarifying the origin of this extra capacity by addressing some fundamental questions regarding reversible anionic redox in high-potential electrodes for Li-ion batteries. First, the ability of the system to stabilize the oxygen holes generated by Li-removal and to achieve a reversible oxo- to peroxo-like (2O2-/(O2)n-) transformation is elucidated by means of a metal-driven reductive coupling mechanism. The penchant of the system for undergoing this reversible anionic redox or releasing O2 gas is then discussed in regards to experimental results for 3d- and 4d-based Li2MO3 phases. Robust indicators are built as tools to predict which materials in the Li-rich TM-oxides family will undergo efficient and reversible anionic redox. The present finding provides insights into new directions to be explored for the development of high-energy density materials for Li-ion batteries.
Published: 2016
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54. A Fully Ordered Triplite, LiCuSO 4 F

Author: Marie-Liesse Doublet, Jean-Marie Tarascon, Meiling Sun, Gwenaëlle Rousse, Daniel Alves Dalla Corte, Saubanère Matthieu, 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), 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 de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Muséum national d'Histoire naturelle (MNHN)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de recherche pour le développement [IRD] : UR206-Centre National de la Recherche Scientifique (CNRS), Laboratoire de physique de la matière condensée (LPMC), École polytechnique (X)-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), ANR-12-PRGE-0005,HIPOLITE,Development of New High Voltage Positive Electrodes for Sustainable Li-Ion Batteries(2012), 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, 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), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de recherche pour le développement [IRD] : UR206-Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS), 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, General Chemical Engineering, Materials Chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, 01 natural sciences, ComputingMilieux_MISCELLANEOUS, 0104 chemical sciences
Abstract: International audience
Published: 2016
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55. Strong oxygen participation in the redox governing the structural and electrochemical properties of Na-rich layered oxide <tex>Na_{2}IrO_{3}$</tex>

Author: Romain Dugas, Karel H. W. van den Bos, Eric McCalla, Arnaud J. Perez, Dmitry Batuk, Erik J. Berg, Gustaaf Van Tendeloo, Danielle Gonbeau, Artem M. Abakumov, Marie-Liesse Doublet, Jean-Marie Tarascon, Dominique Foix, Gwenaëlle Rousse, Matthieu Saubanère, Chaire Chimie du solide et énergie, 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)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU), University of Antwerp (UA), 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), 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, Paul Scherrer Institute (PSI), Skolkovo Institute of Science and Technology [Moscow] (Skoltech), 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 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: Chemistry, General Chemical Engineering, Physics, Inorganic chemistry, Cationic polymerization, Oxide, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Redox, 0104 chemical sciences, Metal, chemistry.chemical_compound, X-ray photoelectron spectroscopy, Formula unit, visual_art, Phase (matter), Materials Chemistry, visual_art.visual_art_medium, 0210 nano-technology
Abstract: International audience; The recent revival of the Na-ion battery concept has prompted intense activities in the search for new Na-based layered oxide positive electrodes. The largest capacity to date was obtained for a Na-deficient layered oxide that relies on cationic redox processes only. To go beyond this limit, we decided to chemically manipulate these Na-based layered compounds in a way to trigger the participation of the anionic network. We herein report the electrochemical properties of a Na-rich phase Na2IrO3, which can reversibly cycle 1.5 Na+ per formula unit while not suffering from oxygen release nor cationic migrations. Such large capacities, as deduced by complementary XPS, X-ray/neutron diffraction and transmission electron microscopy measurements, arise from cumulative cationic and anionic redox processes occurring simultaneously at potentials as low as 2.7 V vs Na+/Na. The inability to remove more than 1.5 Na+ is rooted in the formation of an O1-type phase having highly stabilized Na sites as confirmed by DFT calculations, which could rationalize as well the competing metal/oxygen redox processes in Na2IrO3. This work will help to define the most fertile directions in the search for novel high energy Na-rich materials based on more sustainable elements than Ir.
Published: 2016
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56. Atomistic Modeling of Electrode Materials for Li-Ion Batteries: From Bulk to Interfaces

Author: Marie-Liesse Doublet, Jean-Sébastien Filhol, Matthieu Saubanère, 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), Springer London Heidelberg New York Dordrecht, 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: Electrode material, Materials science, Photovoltaic system, Complex system, Nanotechnology, 02 engineering and technology, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, Energy storage, 13. Climate action, 0103 physical sciences, Energy materials, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Energy transformation, Fuel cells, Hydraulic accumulator, 010306 general physics, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: In the field of energy materials, the computational modeling of electrochemical devices such as fuel cells, rechargeable batteries, photovoltaic cells, or photo-batteries that combine energy conversion and storage represent a great challenge for theoreticians. Given the wide variety of issues related to the modeling of each of these devices, this chapter is restricted to the study of rechargeable batteries (accumulators) and, more particularly, Li-ion batteries. The aim of this chapter is to emphasize some of the key problems related to the theoretical and computational treatment of these complex systems and to present some of the state-of-the-art computational techniques and methodologies being developed in this area to meet one of the greatest challenges of our century in terms of energy storage.
Published: 2016
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57. Activation of surface oxygen sites on an iridium-based model catalyst for the oxygen evolution reaction

Author: Matthieu Saubanère, Walid Dachraoui, Jean-Marie Tarascon, Marie-Liesse Doublet, Martial Duchamp, Arnaud Demortière, Alexis Grimaud, 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), 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), 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), 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), Forschungszentrum Jülich Peter Grünberg Institute (PGI-6), Forschungszentrum Jülich Peter Grünberg Institute, 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), Université de Picardie Jules Verne (UPJV)-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), 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), and Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)
Subjects: Renewable Energy, Sustainability and the Environment, Oxygen evolution, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, Active surface, 010402 general chemistry, 021001 nanoscience & nanotechnology, Photochemistry, Electrocatalyst, 01 natural sciences, Oxygen, Ruthenium oxide, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Catalysis, Fuel Technology, chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], [CHIM]Chemical Sciences, Iridium, 0210 nano-technology, Surface reconstruction
Abstract: International audience; The oxygen evolution reaction (OER) is of prime importance in multiple energy storage devices, however, deeper mechanistic understanding is required in order to design enhanced electrocatalysts for the reaction. Current understanding of the OER mechanism based on oxygen adsorption on a metallic surface site fails to fully explain the activity of iridium and ruthenium oxide surfaces, and the drastic surface reconstruction observed for the most active OER catalysts. Here we demonstrate, using La 2 LiIrO 6 as a model catalyst, that the exceptionally high activity found for Ir-based catalysts arises from the formation of active surface oxygen atoms that act as electrophilic centres for water to react. Moreover, we observe with the help of transmission electron microscopy drastic surface reconstruction and iridium migration from the bulk to the surface. Therefore, we establish a correlation between surface activity and surface stability for OER catalysts which is rooted in the formation of surface reactive oxygen.
Published: 2016
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58. Physical Multiscale Modeling and Numerical Simulation of Electrochemical Devices for Energy Conversion and Storage

Author: Wolfgang G. Bessler, Marie-Liesse Doublet, and Alejandro A. Franco
Subjects: Materials science, Computer simulation, 020209 energy, 0202 electrical engineering, electronic engineering, information engineering, Electronic engineering, Mechanical engineering, Energy transformation, 02 engineering and technology, 021001 nanoscience & nanotechnology, 0210 nano-technology, Electrochemistry, Multiscale modeling
Published: 2016
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59. (Invited) The Paradox of High-Energy Density Materials for Li-Ion Batteries

Author: Marie-Liesse Doublet, Matthieu Saubanere, and Jean Vergnet
Abstract: Increasing the energy density of cathode materials is a central goal of the ongoing research in Li-ion batteries. This implies improving simultaneously the capacity and the potential of the materials used at the positive electrode of the electrochemical device. While the electrochemical potential is well controlled through an appropriate choice of the redox centre involved in the Li-driven electrochemical reactions, the increase of capacity appears more difficult to achieve without penalizing the material structural stability.[1-3] So far, materials showing the highest energy densities are the Li-rich layered transition metal oxides (LLOs) for which a cumulative cationic and anionic redox activity has been demonstrated. Ever since, numerous materials have been synthesized with various combinations of 3d, 4d, 5d or non transition metals [4-6] and different mechanisms have been proposed to rationalize their electrochemical activity vs. Li or Na with no real consensus about the directions to follow to overcome the structural instability that often comes along with the anionic process. In this paper, we review the different interpretations proposed in the literature to address the fundamental questions of increasing both the potential and the capacity of current positive electrodes with the hope that a common language will help in clarifying the relationship between the material electronic structure, the potential, the (extra)-capacity and the consequences of high-energy-density on the material structural stability. This unified picture highlights that a trade-off needs to be found for the development of high-energy-density materials for alkali-ion batteries. References: [1] Zhao, C., Wang, Q., Lu, Y., Hu, Y.-S., Li, B. & Chen, L. Review on anionic redox for high-capacity lithium- and sodium-ion batteries. J. Phys. Appl. Phys. 50, 183001 (2017). [2] Yabuuchi, N. Solid-state Redox Reaction of Oxide Ions for Rechargeable Batteries. Chem. Lett. 46, 412 (2017). [3] Li, B. & Xia, D. Anionic Redox in Rechargeable Lithium Batteries. Adv. Mater. 1701054 (2017). [4] Yabuuchi, N., et al.. High-capacity electrode materials for rechargeable lithium batteries: Li3NbO4-based system with cation-disordered rocksalt structure. Proc. Natl. Acad. Sci. 112, 7650 (2015). Takeda N. et al. Journal of Power Sources 367, 122 (2017). [5] House, R. et al. Lithium manganese oxyfluoride as a new cathode material exhibiting oxygen redox, Energy & Envir. Sci. Accepted (2018). [6] Maitra, U; Oxygen redox chemistry without excess alkali-metal ions in Na2/3[Mg0.28Mn0.72]O2 Nat. Chem. 10 (2018) online. [7] a) Saubanère, M., McCalla, E., Tarascon, J.-M. & Doublet, M.-L. The intriguing question of anionic redox in high-energy density cathodes for Li-ion batteries. Energy Env. Sci 9, 984–991 (2016). [8] Xie, Y., Saubanère, M. & Doublet, M.-L. Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries. Energy Env. Sci 10, 266–274 (2017).
Published: 2018
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60. Reversible Sodium and Lithium Insertion in Iron Fluoride Perovskites

Author: Andréa Martin, Marie-Liesse Doublet, Erhard Kemnitz, Nicola Pinna, Humboldt-Universität zu Berlin, 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), Institut für Chemie and IRIS Adlershof Humboldt-Universität zu Berlin, 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 ), Humboldt Universität zu Berlin, 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, Sodium, Inorganic chemistry, [ PHYS.COND.CM-MS ] Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, Biomaterials, chemistry, Iron fluoride, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Electrochemistry, Lithium, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract: International audience
Published: 2018
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61. Redox mechanism in the NiP2 electrode for Li-ion batteries: A DFT study coupled with local chemical bond analyses

Author: Frédéric Lemoigno, J. Bernardi, Marie-Liesse Doublet, 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, Inorganic chemistry, General Engineering, General Physics and Astronomy, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Tetragonal crystal system, chemistry, Chemical bond, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], General Materials Science, Lithium, Reactivity (chemistry), Density functional theory, 0210 nano-technology, Ternary operation, Monoclinic crystal system
Abstract: Li reactivity of the monoclinic NiP2 electrode is investigated through first-principles density functional theory calculations and local chemical bond analysis. The stability of various Li x NiP2 is studied with respect to the conversion reaction $${\text{NiP}}_{\text{2}} + {\text{6Li}} \to {\text{2Li}}_{\text{3}} + {\text{Ni}}^\circ $$ . The T = 0K Li x NiP2 phase stability diagram, as obtained, reveals that several ternary phases of lithium composition Li2NiP2 can be electrochemically achieved upon reduction. They correspond to monoclinic or tetragonal structures in which Ni adopts a square-planar (D4h-Li2NiP2) or a pseudo-tetrahedral (Td-Li2NiP2) environment. A local chemical bond analysis suggests that D4h–Li2NiP2 would result from an interlayer P–P bond breaking induced by a two-phase (P redox) process, while Td-Li2NiP2 would result from a Jahn–Teller distortion associated with a single-phase (Ni–P redox) process.
Published: 2008
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62. Structural, magnetic and redox properties of a new cathode material for Li-ion batteries: the iron-based metal organic framework

Author: Marie-Liesse Doublet, C. Combelles, 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: Chemistry, Magnetism, General Chemical Engineering, Inorganic chemistry, General Engineering, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Redox, Cathode, 0104 chemical sciences, Ion, law.invention, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Cathode material, law, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], General Materials Science, Metal-organic framework, Density functional theory, 0210 nano-technology
Abstract: International audience; The iron-based metal organic framework (MOF) presently studied is the first example of MOF showing a reversible electrochemical Li insertion with a very good cycling life. Its potential application as a cathode material in Li-ion battery is nevertheless curbed by a rather poor capacity of 70 mAh/g. To figure out the origin of this limited insertion, first-principles density functional theory (DFT)+U calculations were performed. The results show that FeIII{OH(BDC)} is a weak anti-ferromagnetic charge transfer insulator at T=0 K with iron in the high-spin S=5/2 state. In agreement with the absence of electronic delocalisation along the inorganic chains, lithium insertion leads to the stabilisation of a FeII/FeIII mixed-valence state of class I or II in the Robin–Day classification, whatever the Li sites considered in the calculations. Among these Li sites, the most probable site I (OH-Li) and site II (O=CO-Li) are shown to induce incompatible structural changes on the reduced Li0.5Fe{OH(BDC)} form that could be at the origin of the small capacity measured for this compound.
Published: 2007
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63. Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries

Author: Dominique Foix, Jean-Marie Tarascon, Marie-Liesse Doublet, Artem M. Abakumov, Eric McCalla, Erik J. Berg, Robert Dominko, Matthieu Saubanère, Danielle Gonbeau, Gustaaf Van Tendeloo, Gwenaëlle Rousse, Petr Novák, 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), National Institute of Chemistry, Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Chaire Chimie du solide et énergie, 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)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU), EMAT, University of Antwerp, University of Antwerp (UA), Center for Electrochemical Energy Storage, Skolkovo Institute of Science and Technology, 3 Nobel Street, 143026 Moscow, Russia., 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), Institut Pluridisciplinaire de Recherche sur l'Environnement et les Matériaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Centre National de la Recherche Scientifique (CNRS), Paul Scherrer Institute (PSI), Institut de minéralogie, de physique des matériaux et de cosmochimie (IMPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de recherche pour le développement [IRD] : UR206-Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS), EMAT, 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 de Chimie du CNRS (INC)-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), Skolkovo Institute of Science and Technology [Moscow] (Skoltech), 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), Muséum national d'Histoire naturelle (MNHN)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de recherche pour le développement [IRD] : UR206-Centre National de la Recherche Scientifique (CNRS), and Institut pluridisciplinaire de recherche sur l'environnement et les matériaux (IPREM)
Subjects: Crystallography, Multidisciplinary, Transmission electron microscopy, Chemistry, Neutron diffraction, Energy density, Cationic polymerization, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], High capacity, Nanotechnology, Engineering sciences. Technology, Redox, Ion
Abstract: Peering into cathode layered oxides The quest for better rechargeable batteries means finding ways to pack more energy into a smaller mass or volume. Lithium layered oxides are a promising class of materials that could double storage capacities. However, the design of safe and long-lasting batteries requires an understanding of the physical and chemical changes that occur during redox processes. McCalla et al. used a combination of experiments and calculations to understand the formation of O-O dimers, which are key to improving the properties of these cathode materials. Science , this issue p. 1516
Published: 2015
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64. ChemInform Abstract: Li2Cu2O(SO4)2: A Possible Electrode for Sustainable Li-Based Batteries Showing a 4.7 V Redox Activity vs Li+/Li0

Author: Marie-Liesse Doublet, Meiling Sun, Matthieu Saubanère, Juan Rodríguez-Carvajal, Jean-Marie Tarascon, Gwenaëlle Rousse, Gustaaf Van Tendeloo, and Artem M. Abakumov
Subjects: Chemical engineering, Chemistry, Phase (matter), Electrode, Crucible, General Medicine, Ball mill, Stoichiometry, Redox Activity
Abstract: Phase pure Li2Cu2O(SO4)2 is prepared by ball milling and heating of stoichiometric amounts of Li2O and dried CuSO4 under Ar (alumina crucible, 400 °C, 4 d).
Published: 2015
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65. Influence of polymorphism on the electrochemical behavior of MxSb negative electrodes in Li/Na batteries

Author: Marie-Liesse Doublet, Matthieu Saubanère, Frédéric Lemoigno, Mouna Ben Yahia, 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), RS2E, 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, Chemistry, Li/Na-ion battery, Energy Engineering and Power Technology, Ionic bonding, [CHIM.MATE]Chemical Sciences/Material chemistry, Electrochemistry, DFT calculations, Madelung constant, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, Polymorphism (materials science), Electrode, Density functional theory, Chemical stability, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, Selectivity
Abstract: Recently, different and unexpected electrochemical behaviours have been demonstrated for MxSb electrodes (M = Li, Na) in Li/Na ion batteries. Despite a similar thermodynamic stability of the hexagonal and cubic polymorphs of Li3Sb, mostly cubic Li3Sb is observed at the end of discharge. In contrast, mostly the hexagonal Na3Sb polymorph is observed when cycling the Na/Sb, in agreement with its higher thermodynamic stability compared to the cubic polymorph. This polymorph selectivity is here investigated by means of simple thermodynamic and electrostatic considerations using first-principles Density Functional Theory (DFT) calculations. We show that the Na-based polymorphs are more ionic than their Li-based homologues, despite less ionic Na/Sb interactions. We establish a direct correlation between the relative compactness and stability of the M3Sb polymorphs to rationalize the preference of the hexagonal structure type for the most ionic compounds of the M3Sb series (M = Li, Na, K, Rb, Cs). The M−Sb interactions are further linked to the different electrochemical behaviours of the MxSb electrodes through Madelung constant calculations. This method is based on the knowledge of only one given MxSb composition and thus allows rationalizing the different intermediate compositions achieved through electrochemical cycling. To validate our method, we finally provide the first-principles computed phase stability diagrams which further reveal two new phases for both Li–Sb and Na–Sb systems.
Published: 2015
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66. Reversible Li-Intercalation through Oxygen Reactivity in Li-Rich Li-Fe-Te Oxide Materials

Author: Jean-Marie Tarascon, Florent Lepoivre, Danielle Gonbeau, Gustaaf Van Tendeloo, Benedikt Klobes, Eric McCalla, Marie-Liesse Doublet, Moulay Tahar Sougrati, Petr Novák, Raphaël P. Hermann, Annigere S. Prakash, Gwenaëlle Rousse, Sathiya Mariyappan, Erik J. Berg, Artem M. Abakumov, Dominique Foix, Matthieu Saubanère, Chaire Chimie du solide et énergie, 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)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU), Department of Internal Medicine, Albert Schweitzer Hospital, 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), EMAT, University of Antwerp, University of Antwerp (UA), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Pluridisciplinaire de Recherche sur l'Environnement et les Matériaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Centre National de la Recherche Scientifique (CNRS), Jülich Centre for Neutron Science (JCNS - PGI, JARA-FIT), Peter Grünberg Institut, Université Pierre et Marie Curie - Paris 6 (UPMC), 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), Inst Plant Mol Biol, Ctr Biol, CZ-37005, Czech Academy of Sciences [Prague] (CAS), Department of Biology (University of Antwerp), Faculté des Sciences, Université de Liège, 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), 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), Institut pluridisciplinaire de recherche sur l'environnement et les matériaux (IPREM), Peter Grünberg Institut (PGI), and Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Renewable Energy, Sustainability and the Environment, Physics, Inorganic chemistry, Intercalation (chemistry), Oxide, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, Condensed Matter Physics, Oxygen, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Chemistry, chemistry.chemical_compound, chemistry, Materials Chemistry, Electrochemistry, Reactivity (chemistry), ComputingMilieux_MISCELLANEOUS
Abstract: Lithium-rich oxides are a promising class of positive electrode materials for next generation lithium-ion batteries, and oxygen plays a prominent role during electrochemical cycling either by forming peroxo-like species and/or by irreversibly forming oxygen gas during first charge. Here, we present Li-Fe-Te-O materials which show a tremendous amount of oxygen gas release. This oxygen release accounts for nearly all the capacity during the first charge and results in vacancies as seen by transmission electron microscopy. There is no oxidation of either metal during charge but significant changes in their environments. These changes are particularly extreme for tellurium. XRD and neutron powder diffraction both show limited Changes during cycling and no appreciable change in lattice parameters. A density functional theory study of this material is performed and demonstrates that the holes created on some of the oxygen atoms upon oxidation are partially stabilized through the formation of shorter O-O bonds, i.e. (O-2)(n-) species which on further delithiation show a spontaneous O-2 de-coordination from the cationic network and migration to the now empty lithium layer. The rate limiting step during charge is undoubtedly the diffusion of oxygen either out along the lithium layer or via columns of oxygen atoms. (C) 2015 The Electrochemical Society. All rights reserved.
Published: 2015
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67. <tex>Li_{2}Cu_{2}O(SO_{4})_{2}$</tex>: a possible electrode for sustainable Li-based batteries showing a 4.7 V redox activity vs <tex>Li^{+}/Li^{0}$</tex>

Author: Gwenaëlle Rousse, Gustaaf Van Tendeloo, Jean-Marie Tarascon, Marie-Liesse Doublet, Matthieu Saubanère, Juan Rodríguez-Carvajal, Meiling Sun, and Artem M. Abakumov
Subjects: inorganic chemicals, Chemistry, Ligand, General Chemical Engineering, Physics, Inorganic chemistry, General Chemistry, Crystal structure, Electrochemistry, Redox, Redox Activity, Phase (matter), Electrode, Materials Chemistry, Reactivity (chemistry)
Abstract: Li-ion batteries rely on the use of insertion positive electrodes with performances scaling with the redox potential of the 31) metals accompanying Liuptake/removal. Although not commonly studied, the Cu2+/Cu3+ redox potential has been predicted from theoretical calculations to possibly offer a high operating voltage redox couple. We herein report the synthesis and crystal structure of a hitherto-unknown oxysulfate phase, Li2Cu2O(SO4)(2), which contains infinite edgesharing CuO4 chains and presents attractive electrochemical redox activity with respect to Li+/Li, namely amphoteric characteristics. Li2Cu2O(SO4)(2) shows redox activity at 4.7 V vs Li+/Li corresponding to the oxidation of Cu2+ to Cu3+ enlisting ligand holes and associated with the reversible uptake-removal of 0.3 Li. Upon reduction, this compound reversibly uptakes similar to 2 Li at an average potential of about 2.5 V vs Li+/Li, associated with the Cu2+/Cu+ redox couple. The mechanism of the reactivity upon reduction is discussed in detail, with particular attention to the occasional appearance of an oscillation wave in the discharge profile. Our work demonstrates that Cu-based compounds can indeed be fertile scientific ground in the search for new high-energy-density electrodes.
Published: 2015

68. Origin of voltage decay in high-capacity layered oxide electrodes

Author: Marie-Liesse Doublet, Matthieu Saubanère, Danielle Gonbeau, Prakash As, VanTendeloo G, Artem M. Abakumov, Laisa Cp, Jean-Marie Tarascon, Hervé Vezin, Kannadka Ramesha, Gwenaëlle Rousse, Dominique Foix, Mariyappan Sathiya, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), EMAT, University of Antwerp, University of Antwerp (UA), Institut pluridisciplinaire de recherche sur l'environnement et les matériaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-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)-Université Paris Diderot - Paris 7 (UPD7)-Institut de Physique du Globe de Paris (IPG Paris)-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), CSIR (CSIR), CSIR, 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), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-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), Institut Pluridisciplinaire de Recherche sur l'Environnement et les Matériaux (IPREM), Université Pierre et Marie Curie - Paris 6 (UPMC)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), 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), 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 Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL)
Subjects: Metal ions in aqueous solution, Analytical chemistry, Oxide, Li-ion batteries, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Ion, Metal, chemistry.chemical_compound, X-ray photoelectron spectroscopy, General Materials Science, Ionic radius, Chemistry, Physics, Mechanical Engineering, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Mechanics of Materials, Transmission electron microscopy, 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
Abstract: International audience; Although Li-rich layered oxides (Li1+xNiyCozMn1−x−y−zO2 > 250 mAh g−1) are attractive electrode materials providing energy densities more than 15% higher than today’s commercial Li-ion cells, they suffer from voltage decay on cycling. To elucidate the origin of this phenomenon, we employ chemical substitution in structurally related Li2RuO3 compounds. Li-rich layered Li2Ru1−yTiyO3 phases with capacities of ~240 mAh g−1 exhibit the characteristic voltage decay on cycling. A combination of transmission electron microscopy and X-ray photoelectron spectroscopy studies reveals that the migration of cations between metal layers and Li layers is an intrinsic feature of the charge–discharge process that increases the trapping of metal ions in interstitial tetrahedral sites. A correlation between these trapped ions and the voltage decay is established by expanding the study to both Li2Ru1−ySnyO3 and Li2RuO3; the slowest decay occurs for the cations with the largest ionic radii. This effect is robust, and the finding provides insights into new chemistry to be explored for developing high-capacity layered electrodes that evade voltage decay.
Published: 2015
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69. (BETS)2[RuX5NO] (X = Cl, Br): An Explanation of Different Conductive Properties Through Structural and Spectroscopic Studies

Author: Marie-Liesse Doublet, Lydie Valade, Kane Jacob, A. Glaria, Jean-François Lamère, D. de Caro, Isabelle Malfant, Antoine Zwick, S. Vincendeau, and B. Garreau de Bonneval
Subjects: Materials science, Bromine, business.industry, chemistry.chemical_element, Activation energy, Condensed Matter Physics, Atomic and Molecular Physics, and Optics, chemistry.chemical_compound, symbols.namesake, Semiconductor, chemistry, Electrical resistivity and conductivity, Chlorine, symbols, Physical chemistry, General Materials Science, Raman spectroscopy, business, Derivative (chemistry), Stoichiometry
Abstract: (BETS)2[RuX5NO] (X=Cl, Br) exhibit an identical 2:1 stoichiometry. However, while the chlorine derivative shows an insulating behavior, the bromine behaves as a semiconductor with very small activation energy (0.03 eV). The different electrical behaviors are analyzed through the use of a detailed study of structural data and analysis of Raman spectra
Published: 2006
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70. Electrochemical Reactivity and Design of NiP2 Negative Electrodes for Secondary Li-Ion Batteries

Author: Marie-Liesse Doublet, Mathieu Morcrette, Jean-Marie Tarascon, Loic Dupont, Frédéric Gillot, Laure Monconduit, Simeon Boyanov, 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), 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 Projet européen ALISTORE
Subjects: General Chemical Engineering, Inorganic chemistry, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, General Medicine, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, 7. Clean energy, 0104 chemical sciences, Crystallography, chemistry, Transmission electron microscopy, Formula unit, Phase (matter), Electrode, Materials Chemistry, Lithium, 0210 nano-technology, High-resolution transmission electron microscopy, Monoclinic crystal system
Abstract: International audience; We report the electrochemical study of cubic and monoclinic NiP2 polymorphs toward Li, as a candidate for anodic applications for Li-ion batteries. We found that the monoclinic form is the most attractive one performance-wise. Monoclinic NiP2 can reversibly uptake 5 lithium per formula unit, leading to reversible capacities of 1000 mAh/g at an average potential of 0.9 V vs Li+/Li°. From complementary X-ray diffraction (XRD) and HRTEM (high-resolution transmission electron microscopy) measurements, it was shown that, during the first discharge, the cubic phase undergoes a pure conversion process (NiP2 + 6 Li+ + 6e- f Ni° + 2Li3P) as opposed to a sequential insertion-conversion process for monoclinic NiP2. Such a different behavior rooted in subtle structural changes was explained through electronic structure calculations. Once the first discharged is achieved, both phases were shown to react with Li through a classical conversion process. More importantly, we report a novel way to design NiP2 electrodeswith enhanced capacity retention and rate capabilities. It consists in growing the monoclinic NiP2 phase,through a vapor-phase transport process, on a commercial Ni-foam commonly used in Ni-based alkaline batteries. These new self-supported electrodes, based on chemically made interfaces, offer new opportunities to fully exploit the capacity gains provided by conversion reactions
Published: 2005
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71. Progress in the lithium insertion mechanism in Cu3P

Author: M. Morcrette, Marie-Liesse Doublet, Marie-Pierre Bichat, Laure Monconduit, Frédéric Favier, and B. Mauvernay
Subjects: Phosphide, General Chemical Engineering, Inorganic chemistry, Extraction (chemistry), General Engineering, General Physics and Astronomy, chemistry.chemical_element, Electrochemistry, Copper, Redox, chemistry.chemical_compound, chemistry, visual_art, visual_art.visual_art_medium, General Materials Science, Lithium, Ceramic, Solid solution
Abstract: Copper phosphide, Cu3P has been synthesized using a ceramic route, and its electrochemical behaviour versus lithium has been studied studied galvanostatic and potentiodynamic measurements and in situ X-ray diffraction analysis. The insertion/extraction mechanism proceeds with the formation of at least three different LixCu3−xP (x=1, 2, 3) phases. The electrochemical behaviour of Cu3P samples obtained from ceramic and solvothermal syntheses are compared to further understanding of the complex redox mechanism occurring during insertion/extraction. First-principle electronic structure calculations show that discharge probably begins with the formation of a solid solution LixCu3−yP (x
Published: 2005
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72. The LixMPn4 phases (M/Pn = Ti/P, V/As): new negative electrode materials for lithium ion rechargeable batteries

Author: M. Morcrette, Marie-Liesse Doublet, Marie-Pierre Bichat, Laure Monconduit, Frédéric Favier, and Frédéric Gillot
Subjects: Diffraction, General Chemical Engineering, Inorganic chemistry, Analytical chemistry, chemistry.chemical_element, Electrochemistry, Lithium-ion battery, Amorphous solid, Ion, chemistry.chemical_compound, chemistry, Ternary compound, Lithium, Ternary operation
Abstract: Li x TiP 4 ternary phases ( x =7 and 9) show very close electrochemical behaviors versus lithium compared to the previously reported Li 9 VAs 4 and Li 7 VP 4 . Up to seven lithium ions reversibly react with Li 9 TiP 4 , leading to specific and volumetric capacities of 970 mAh/g and 1650 mAh/cm 3 , respectively, at average potentials close to 1 V. Galvanostatic and potentiodynamic experiments reveal that lithium extraction/insertion follow different mechanisms: a two-phase process is evidenced on charge whereas a more complex process is achieved on discharge. Besides, in situ X-ray diffraction (XRD) patterns show that both Li 9 TiP 4 and Li 9 VAs 4 undergo a reversible crystalline to amorphous structural phase transition upon cycling.
Published: 2004
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73. Redox-Induced Structural Change in Anode Materials Based on Tetrahedral (MPn4)x- Transition Metal Pnictides

Author: Marie-Liesse Doublet, M. P. Bichat, Frédéric Lemoigno, Laure Monconduit, Frédéric Gillot, M. Morcrette, and Frédéric Favier
Subjects: chemistry.chemical_classification, Battery (electricity), Materials science, General Chemical Engineering, General Chemistry, Polymer, Electronic structure, Redox, Anode, Crystallography, Structural change, Transition metal, chemistry, Electrode, Materials Chemistry
Abstract: The study presents a combined experimental and computational study of Li+ extraction/insertion mechanisms in cubic-fcc transition metal pnictides LixMPn4 (MPn = TiP, VP, VAs). Exhibiting high specific capacities (Cmax = 830 mA h g-1) at a potential close to 1 V, these materials have been recently proposed as promising negative electrode materials for Li-ion battery. In situ XRD and first-principle electronic structure calculations including full structural relaxations are used to correlate the reversible structural phase transition observed in oxidation/reduction, to a loss/reconstruction of the unit cell fcc symmetry. The mechanism is rationalized in terms of a M−Pn bond contraction/elongation of the tetrahedral (MPn4)x- electronic entities, on which initial structures are built. This unusual redox-induced mechanism occurs without any significant electrode volume change, thus solving one of the major drawbacks of anodes.
Published: 2004
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74. New salts derived from organic donor molecules with long-living excited states counter-ions

Author: Christophe Faulmann, Luca Pilia, Isabelle Malfant, B. Garreau de Bonneval, M. E. Sanchez, L. Kushch, Patrick Cassoux, and Marie-Liesse Doublet
Subjects: Chemistry, Stereochemistry, Mechanical Engineering, Metals and Alloys, Crystal structure, Electronic structure, Condensed Matter Physics, Photochemistry, Electronic, Optical and Magnetic Materials, Ion, Photochromism, Radical ion, Mechanics of Materials, Excited state, Materials Chemistry, Molecule, Electronic band structure
Abstract: The synthesis, X-ray and electronic structures of electroconducting radical ion salts based on organic donors (BETS and EDX-DMTTF (X=O, Se)) with inorganic counter-ions having photochromic properties are reported.
Published: 2003
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75. The LixVPn4 Ternary Phases (Pn = P, As): Rigid Networks for Lithium Intercalation/Deintercalation

Author: Marie-Liesse Doublet, and Frédéric Gillot, Frédéric Lemoigno, and Laure Monconduit
Subjects: General Chemical Engineering, Intercalation (chemistry), Inorganic chemistry, chemistry.chemical_element, General Chemistry, Crystal structure, Electronic structure, Crystallography, chemistry, Transition metal, Covalent bond, Formula unit, Materials Chemistry, Lithium, Ternary operation
Abstract: We present the ternary phases LixVPn4 (Pn = P, As) as new materials for the negative electrode in lithium-ion batteries. Associated with a large variation of lithium content per formula unit (3 ≤ x ≤ 7.5 for P and 3 ≤ x ≤ 11 for As), these materials show a higher specific capacities in their first charge/discharge cycle than the graphite (550 mA·h/g for Pn = P and 530 mA·h/g for Pn = As vs 372 m·Ah/g for Cgr) and open new routes for the design of new types of rechargeable Li-ion batteries. High-temperature syntheses, X-ray diffraction analyses, and first-principle electronic structure calculations give evidence of remarkable stability of the LixVPn4 crystal structure upon various lithium compositions. Owing to rather strong covalent V−Pn bonds, the host matrixes behave as structurally stable networks of weakly interacting tetrahedra, able to store (respectively, release) a large number of additional electrons (correlatively with the intercalation (respectively, deintercalation) of Li+ in the host matrix) ...
Published: 2002
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76. Requirements for Reversible Extra-Capacity in Li-Rich Layered Oxides for Li-Ionbatteries

Author: Ying Xie, Matthieu Saubanere, and Marie-Liesse Doublet
Abstract: The structural stability and redox mechanism of Li-rich transition metal oxides (LLO) are two very important aspects for high energy density. The former is related to the irreversible loss of lattice oxygen and capacity fading during cycling, while the latter determines the overall capacity of the materials. This paper aims at clarifying the factors governing the structural stability, the extra capacity and the redox mechanism of LLOs upon Li-removal. The results show that the structural stability against oxygen vacancy formation is improved with increasing M-O covalency, while it decreases with increasing thed-shell electron number and with electrochemical extraction of lithium from the lattice. The redox mechanism of Li2-xMO3 electrodes formed by 3d metals or by heavier metals with ad0electronic configuration is related to the electron depletion from the oxygen lone-pairs (localized and non-bonding O(2p) states) leading to an irreversible anionic redox ending with the reductive elimination of O2 upon cycling. For these phases, long-term cycling is predicted to be very unlikely due to the irreversible loss of lattice oxygen upon charging. For the electrodes formed by 4d and 5d metals with intermediate dnelectronic configurations (n ≥2), reversible cationic and anionic redox activities are predicted, therefore enabling reversible extra-capacities. The very dierent redox mechanisms exhibited by Li2-xMO3electrodes are then linked to the delicate balance between the Coulomb repulsions (Uterm) and the M-O bond covalency (Δ term) through the general description of Charge-Transfer vs. Mott-Hubbard insulators. The present findings will provide a uniform guideline for tuning the band structures of Li2MO3phases 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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77. ChemInform Abstract: An Oxysulfate Fe2O(SO4)2Electrode for Sustainable Li-Based Batteries

Author: Artem M. Abakumov, Jean-Marie Tarascon, Matthieu Courty, Meiling Sun, Gwenaëlle Rousse, Gustaaf Van Tendeloo, Marie-Liesse Doublet, and Moulay Tahar Sougrati
Subjects: Chemical engineering, Chemistry, Electrode, Pellets, General Medicine
Abstract: The title oxysulfate is synthesized by keeping FeSO4OH pellets (obtained by heating FeSO4·7H2O in air at 280 °C for 7 d) in air at 465 °C for 4 days.
Published: 2014
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78. New Insights on the Reversible Lithiation Mechanism of TiO2(B) by Operando X-ray Absorption Spectroscopy and X-ray Diffraction Assisted by First-Principles Calculations

Author: Marie-Liesse Doublet, Mouna Ben Yahia, Lorenzo Stievano, Laure Monconduit, Cécile Tessier, Frédéric Lemoigno, Marcus Fehse, Florent Fischer, 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), SAFT [Bordeaux], Société des accumulateurs fixes et de traction (SAFT), 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), 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: Diffraction, X-ray absorption spectroscopy, Absorption spectroscopy, Extended X-ray absorption fine structure, Chemistry, chemistry.chemical_element, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Bond length, Crystallography, General Energy, Chemical bond, ddc:540, X-ray crystallography, Lithium, Physical and Theoretical Chemistry, 0210 nano-technology
Abstract: International audience; Operando X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) measurements provide new insights on the mechanism of lithium insertion into TiO2(B). The investigation of the evolution of electronic, long-range, and local structure during electrochemical cycling indicates a purely monophasic insertion mechanism upon lithium insertion, while global and local structure are only slightly modified. While XRD reflects an anisotropic lattice expansion, EXAFS reveals a wide distribution of Ti–O bond length, in line with the presence of two distinct distorted octahedral Ti environments, in agreement with previous DFT calculations. Upon lithium insertion, these Ti–O coordination shells undergo significant modifications which are enhanced once the insertion of 0.4 Li is exceeded, connoting a two regime process that is in good agreement with the electrochemical signature of this material. DFT calculations and local chemical bond analyses were coupled with experimental results, thus providing additional insights into the structural response of TiO2(B) upon lithiation.
Published: 2014
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79. Conceptual Surface Electrochemistry and New Redox Descriptors

Author: Jean-Sébastien Filhol, 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), 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), 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), 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, Analytical chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Atomic units, Redox, Capacitance, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, General Energy, Chemical physics, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Density functional theory, Physical and Theoretical Chemistry, Physics::Chemical Physics, 0210 nano-technology, Polarization (electrochemistry), Fukui function, Electrochemical potential
Abstract: International audience; This paper aims at enlightening the link between surface properties, conceptual density functional theory (DFT), and electrochemistry. The energy of a metallic charged surface is expanded into classical terms such as electrochemical potential or chemical hardness and into new terms such as electromechanical coupling vector, electrochemical Hessian matrix change, etc. These quantities are shown to be crucial parameters to understand interface electrochemistry and in particular the surface zero-charge potential, the capacitance and its derivatives, and the surface structural polarization at the atomic scale. Furthermore, the Fukui function initially introduced to rationalize molecular reactivity is here shown to directly probe the electrochemical activity of the surface. First, it gives the spatial repartition on the surface of the charge added during an electrochemical step, and second it quantifies the electrochemical parameters of the system: the electrochemical potential and the electromechanical coupling vector mainly arise from the interaction of the Fukui function with the local surface dipole and the nucleus electric field, while the capacitance mostly comes from the Fukui function self-electrostatic interaction. The electrochemical Hessian change matrix controls part of the bond modifications induced by the electrochemical process and directly depends on the Fukui function derivatives with respect to atomic displacements. This description not only allows linking the electrochemical bond modification with conceptual DFT and molecular orbital theories but can also be used quantitatively to extract electrochemical properties from response theory.
Published: 2014
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80. An oxysulfate Fe₂O(SO₄)₂ electrode for sustainable Li-based batteries

Author: Meiling, Sun, Gwenaëlle, Rousse, Artem M, Abakumov, Gustaaf, Van Tendeloo, Moulay-Tahar, Sougrati, Matthieu, Courty, Marie-Liesse, Doublet, and Jean-Marie, Tarascon
Abstract: 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 Fe(3+)/Fe(2+) 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

81. An intuitive and efficient method for cell voltage prediction of lithium and sodium-ion batteries

Author: Sébastien Lebègue, M. Ben Yahia, Marie-Liesse Doublet, Matthieu Saubanère, 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), Cristallographie, Résonance Magnétique et Modélisations (CRM2), Université de Lorraine (UL)-Centre National de la Recherche Scientifique (CNRS), 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), 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: Multidisciplinary, Materials science, Cell voltage, Voltage prediction, General Physics and Astronomy, chemistry.chemical_element, Nanotechnology, General Chemistry, Material Design, Crystal structure, General Biochemistry, Genetics and Molecular Biology, Cathode, law.invention, chemistry, law, Present method, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Li-ion battery, Theory, Lithium, Voltage
Abstract: International audience; The voltage delivered by rechargeable Lithium- and Sodium-ion batteries is a key parameter to qualify the device as promising for future applications. Here we report a new formulation of the cell voltage in terms of chemically intuitive quantities that can be rapidly and quantitatively evaluated from the alkaliated crystal structure with no need of first-principles calculations. The model, which is here validated on a wide series of existing cathode materials, provides new insights into the physical and chemical features of a crystal structure that influence the material potential. In particular, we show that disordered materials with cationic intermixing must exhibit higher potentials than their ordered homologues. The present method is utilizable by any solid-state chemist, is fully predictive and allows rapid assessement of material potentials, thus opening new directions for the challenging project of material design in rechargeable batteries.
Published: 2014
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82. Structure and properties of BETS salts: κ-(BETS)8(Cu2Cl6)(CuCl4), θ-(BETS)2(CuCl2) and (BETS)2(CuCl4)

Author: Christophe Faulmann, Akiko Kobayashi, Patrick Cassoux, T. Courcet, Philippe Guionneau, Natalyia D Kushch, Fabien Granier, Judith A. K. Howard, Heinz Gornitzka, Marie-Liesse Doublet, and Isabelle Malfant
Subjects: biology, Stereochemistry, Fermi surface, General Chemistry, Electronic structure, Crystal structure, ASPH, chemistry.chemical_compound, Crystallography, chemistry, Chlorobenzene, biology.protein, Molecule, Antiferromagnetism, Electronic band structure
Abstract: κ-(BETS) 8 (Cu 2 Cl 6 )(CuCl 4 ) ( 1 ), θ-(BETS) 2 (CuCl 2 ) ( 2 ), (BETS) 2 (CuCl 4 ) ( 3 ) (BETS = bis(ethylenedithio)tetraselenafulvalene) have been prepared by diffusion-electrocrystallisation of BETS and (AsPh 4 ) 2 (Cu 2 Cl 6 ) solutions in chlorobenzene–ethanol. 2 has also been obtained by simple diffusion of BETS and (AsPh 4 ) 2 (Cu 2 Cl 6 ) solutions. 1 and 2 exhibit metal-like behaviour, down to 40 K for 1 and 4 K for 2 . 3 behaves as an insulator. The crystal structures of 1 , 2 , and 3 are determined by X-ray diffraction methods. The structures of 1 (at 140 and 25 K) and 2 are characterised by a strong disorder of their respective anions. The crystal structure of 3 shows an unusual packing of the BETS molecules, consisting of slipped stacked (BETS) 2 dimers, leading to insulating properties. Based on the structures of 1 (at 140 and 25 K), 2 and 3 , molecular and band structure calculations are carried out for the interpretation of the physical behaviours of these phases.
Published: 2001
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83. Synthesis, electrical behaviour, and crystal and electronic band structures of two different phases of the (SMeEt2)[Pd(dmit)2]2 salt. Consequences of cationic disorder on the electrical properties

Author: Christophe Faulmann, B. Garreau de Bonneval, J.-P. Legros, F. Granier, Marie-Liesse Doublet, T. Togonidze, Patrick Cassoux, and Isabelle Malfant
Subjects: Phase transition, Chemistry, Inorganic chemistry, General Chemistry, Crystal structure, Ion, Crystal, Metal, Crystallography, Electron transfer, Electrical resistivity and conductivity, visual_art, Materials Chemistry, visual_art.visual_art_medium, Electronic band structure
Abstract: The previously mentioned (SMeEt2)[Pd(dmit)2]2 (1) and the new (SMeEt2)0.5[Pd(dmit)2] (2) phases are obtained by electrocrystallisation of (SMeEt2)2[Pd(dmit)2] in acetonitrile. The crystal structures of 1 and 2 are determined by X-ray diffraction methods, both at room and low temperatures. Though not previously detected, a cation disorder is evidenced in both phases at room temperature which is removed in 1 at low temperatures. Conductivity measurements show a rather smooth metal to insulator transition in the 150–200 K range for 1 whereas 2 behaves as a semiconductor in the whole range of temperature. Under pressure, the transition of 1 is shifted down to lower temperatures and becomes more abrupt. Electronic band structure calculations (by means of the extended Huckel tight-binding model) show that the cation disorder evidenced in 1 is responsible for two different electron transfers occurring from the (SMeEt2)+ cation layers to the two crystallographically independent anion layers, resulting thus in the observed room temperature metal-like behaviour of 1. The ambient pressure phase transition of 1 is shown to be the consequence of a more homogeneous electron transfer, possibly leading to a Mott–Hubbard localised state at low temperatures, as is also the case for 2. Under pressure, the more abrupt phase transition observed in 1 is believed to originate from a different metallic regime.
Published: 2001
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84. Density functional theory analysis of the local chemical bonds in the periodic tantalum dichalcogenides TaX2 (X=S, Se, Te)

Author: Frédéric Lemoigno, S. Remy, and Marie-Liesse Doublet
Subjects: Electron density, Condensed matter physics, Chemistry, Fermi level, General Physics and Astronomy, Electronic structure, Antibonding molecular orbital, symbols.namesake, Chemical bond, Density of states, symbols, Density functional theory, Physical and Theoretical Chemistry, Electronic band structure
Abstract: The electronic structure of layered tantalum dichalcogenides 1T-TaX2 (X=S, Se, Te) have been studied both with the linear muffin tin orbitals-atomic sphere approximation (LMTO-ASA) and the Amsterdam density functional for band (ADF-band) programs. The first code (LMTO) provides band structures, density of states (DOS), and crystal orbitals Hamiltonian populations (COHP) while the second one allows accurate atomic charge calculations by means of a powerful electron density numerical integration. All those analyses were used to rationalize the electronic structures of the three 1T-TaX2 phases, in particular to enlighten the 13×13 structural modulations observed in TaS2 and TaSe2, and to put forward the influence of the local chemical Ta–Te bonds on the relative stability of the 1T-TaTe2 phase vs the distorted monoclinical one. The indirect overlap between the two bands responsible for the metallic properties of TaS2 and TaSe2 has been shown to significantly increase the tantalum d electron count compared to its formal value (d1) leading to a more realistic occupation of the threefolded t2g-like bands involved in the 13×13 instability. Owing to the low electronegative character of Te compared to S and Se, the direct overlap occurring at the Fermi level results in an electron transfer from local Ta–Te bonding states to local Ta–Te antibonding ones yielding a destabilization of the metal–chalcogen bonds.
Published: 2000
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85. Why has 1T-TaTe2 not yet been synthetized? A DFT contribution

Author: Frédéric Lemoigno, Marie-Liesse Doublet, and S. Remy
Subjects: Chemistry, Mechanical Engineering, Metals and Alloys, Crystal structure, Electronic density of states, Electronic structure, Orbital overlap, Condensed Matter Physics, Electronic, Optical and Magnetic Materials, Crystal, Mechanics of Materials, Chemical physics, Ab initio quantum chemistry methods, Computational chemistry, Phase (matter), Materials Chemistry, Density of states
Abstract: Periodical Density Functional (DFT) calculations were done on a hypothetical 1T-TaTe 2 phase in order to understand why this compound has not yet been synthetized. The combined analysis of the density of states and of the crystal orbital overlap populations have disclosed bands interaction that could be at the origin of the non existence of the 1T-TaTe 2 phase.
Published: 1999
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86. Correlation and dimerization effects on the physical behavior of the NR4[Ni(dmit)2]2 charge transfer salts: A density matrix renormalization group study of the quarter-filling t–J model

Author: Marie-Liesse Doublet and Marie-Bernadette Lepetit
Subjects: Physics, Condensed matter physics, business.industry, Density matrix renormalization group, General Physics and Astronomy, Charge (physics), Activation energy, Semiconductor, t-J model, Molecule, Physical and Theoretical Chemistry, Ionization energy, business, Electronic density
Abstract: The present work studies the quasi one-dimensional $Ni(dmit)_2$-based compounds within a correlated model. More specifically, we focus our attention on the composed influence of the electronic dimerization-factor and the repulsion, on the transport properties and the localization of the electronic density in the ground-state. Those properties are studied through the computation of the charge gaps (difference between the ionization potential and the electro-affinity: IP-EA) and the long- and short-bond orders of an infinite quarter-filled chain within a $t-J(t,U)$ model. The comparison between the computed gaps and the experimental activation energy of the semiconductor $NH_2Me_2 [Ni(dmit)_2]_2$ allows us to estimate the on-site electronic repulsion of the $Ni(dmit)_2$ molecule to $1.16eV$.
Published: 1999
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87. Orbital Approach to the Electronic Structure of Solids

Author: Enric Canadell, Marie-Liesse Doublet, Christophe Iung, Enric Canadell, Marie-Liesse Doublet, and Christophe Iung
Subjects: Solids, Electronic structure, Molecular orbitals
Abstract: This book provides an intuitive yet sound understanding of how structure and properties of solids may be related. The natural link is provided by the band theory approach to the electronic structure of solids. The chemically insightful concept of orbital interaction and the essential machinery of band theory are used throughout the book to build links between the crystal and electronic structure of periodic systems. In such a way, it is shown how important tools for understanding properties of solids like the density of states, the Fermi surface etc. can be qualitatively sketched and used to either understand the results of quantitative calculations or to rationalize experimental observations. Extensive use of the orbital interaction approach appears to be a very efficient way of building bridges between physically and chemically based notions to understand the structure and properties of solids.
Published: 2012

88. A new theoretical approach for the electrical properties of TiX2 (X=S, Se, Te) phases with density functional calculations

Author: R. Brec, N. Gallego-Planas, S. Jobic, P. H. T. Philipsen, and Marie-Liesse Doublet
Subjects: education.field_of_study, Condensed matter physics, Chemistry, Population, General Physics and Astronomy, Electronic structure, Orbital overlap, Semimetal, Crystal, Electron transfer, Transition metal, Density functional theory, Physical and Theoretical Chemistry, education
Abstract: The electronic structures of layered transition metal dichalcogenides TiX2 (X=S, Se, Te) have been studied with the Amsterdam Density Functional package for periodic systems (ADF-BAND). The accuracy of this algorithm to calculate the charge transfer between the chalcogens and the metal has been tested at different levels of approximation (local-density approximation, generalized gradient corrections of Becke–Perdew and Perdew–Wang, and quasirelativistic calculations). The total and partial density of states of the three compounds, as well as the crystal orbital overlap population analysis, have been used to rationalize the electronic structure of the systems. The present results show a significant p/d-block band overlap for TiTe2, leading to a Te(5p)→Ti(3d) electron transfer and a metallic behavior. Conversely, owing to the redox competition between the metal and the chalcogens, TiS2 and TiSe2 are predicted to be a semiconductor and a semimetal respectively. These physical properties are discussed in term...
Published: 1998
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89. High Performance Li2Ru1−yMnyO3 (0.2 ≤ y ≤ 0.8) Cathode Materials for Rechargeable Lithium-Ion Batteries: Their Understanding

Author: Jean-Marie Tarascon, Kannadka Ramesha, Gwenaëlle Rousse, Danielle Gonbeau, Mariyappan Sathiya, Marie-Liesse Doublet, K. Hemalatha, Dominique Foix, Annigere S. Prakash, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), CSIR Central Electrochemical Research Institute (CSIR), CSIR, Institut de minéralogie et de physique des milieux condensés (IMPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-Université Paris Diderot - Paris 7 (UPD7)-Institut de Physique du Globe de Paris (IPG Paris)-Centre National de la Recherche Scientifique (CNRS), Institut pluridisciplinaire de recherche sur l'environnement et les matériaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-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 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), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université Pierre et Marie Curie - Paris 6 (UPMC)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Institut Pluridisciplinaire de Recherche sur l'Environnement et les Matériaux (IPREM), 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 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, General Chemical Engineering, Analytical chemistry, chemistry.chemical_element, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Redox, Cathode, 0104 chemical sciences, Ion, law.invention, Ruthenium, chemistry, X-ray photoelectron spectroscopy, law, Materials Chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Lithium, 0210 nano-technology, Voltage, Solid solution
Abstract: International audience; Understanding the origin of the high capacity displayed by Li2MnO3−LiMO2 (M = Ni, Co) composites is essential for improving their cycling and rate capability performances. To address this issue, the Li2Ru1−yMnyO3 series between the iso-structural layered end-members Li2MnO3 and Li2RuO3 was investigated. A complete solid solution was found, with the 0.4 ≤ y ≤ 0.6 members showing sustainable reversible capacities exceeding 220 mAh*g−1 centered around 3.6 V vs Li+/Li. The voltage−composition profiles display a plateau on the first charge as compared to an S-type curve on subsequent discharge which is maintained on the following charges/discharges, with therefore a lowering of the average voltage. We show this profile to evolve upon long cycling due to a structural phase transition as deduced from XRD measurements. Finally we demonstrate, via XPS measurements, the oxidation and reduction of ruthenium (Ru5+/Ru4+) during cycling together with a partial activity of the Mn4+/Mn3+ redox couple. Moreover, we provide direct evidence for the reversibility of the O2− → O− anionic process upon cycling, hence accounting for the high capacity displayed by these materials. This work, by capturing the main redox processes pertaining to these materials, should facilitate their development.
Published: 2013
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90. Origin of the Voltage Hysteresis in the CoP Conversion Material for Li-Ion Batteries

Author: Miran Gaberšček, Marie-Liesse Doublet, Matthieu Saubanère, Anne-Laure Dalverny, Rémi Khatib, 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), Laboratory for Materials Electrochemistry, National Institute of Chemistry, 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), 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), 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: Chemistry, Relaxation (NMR), Mineralogy, Thermodynamics, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 7. Clean energy, 01 natural sciences, Lithium battery, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Ion, Hysteresis, General Energy, Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Physical and Theoretical Chemistry, 0210 nano-technology, Order of magnitude, Phase diagram
Abstract: International audience; The electrochemical activity of the CoP conversion electrode was investigated through the combination of computational and experimental techniques. The carbon-free CoP electrode shows better performances than the carbon-coated electrode, in sharp contrast with the beneficial role of carbon coating reported in many insertion materials. A two-step insertion/conversion process associated with the exchange of 3Li is predicted for this system from the T = 0 K phase stability diagram performed on bulk structures within the DFT framework. The voltage hystereses measured for these two processes through a seven-day relaxation procedure (GITT) are 1 order of magnitude higher for the conversion process (ΔVconvexp = 0.44 V) than for the insertion process (ΔVinsexp = 0.04 V). The various elementary reactions susceptible to occur at the surface of the electrode were investigated by means of surface DFT calculations. This mechanistic study shows that the insertion mechanism is not significantly affected by the electrode nanosizing (ΔVinsth = 0.04 V), while the conversion reaction does. Asymmetric responses are expected upon charge and discharge for this system, due to the growth of different interfaces. This induces different electrochemical equilibriums and then different voltages in charge and discharge. The hysteresis voltage computed for the conversion of LiCoP into Li3P + Co0 is again in very good agreement with experiments (ΔVconvth = 0.41 V). Such results are very encouraging and open new routes to the rationalization of the microscopic mechanisms acting as limiting reactions in electrode materials for Li-ion batteries.
Published: 2013
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91. Electronic Structure of the $\mathsf{\alpha}$-(BEDT-TTF)$\mathsf{_2}$MHg(XCN)$\mathsf{_4}$ (M = Tl, K, NH$\mathsf{_4}$; X = S, Se) and Related Phases. Synthesis and Crystal Structure of the New Stable Organic Metal $\alpha$-(BEDT-TTF)$\mathsf{_2}$TlHg(Se$\mathsf{_{\rm 1-x}}$S$\mathsf{_{\rm x}}$CN)$\mathsf{_4}$ (x = 0.125)

Author: Eduard B. Yagubskii, R. Rousseau, Enric Canadell, Rimma P. Shibaeva, Salavat S. Khasanov, Marie-Liesse Doublet, Nataliya D. Kushch, and L.P. Rozenberg
Subjects: Materials science, General Engineering, Statistical and Nonlinear Physics, Fermi surface, Electron, Crystal structure, Electronic structure, Conductivity, Metal, Crystallography, visual_art, visual_art.visual_art_medium, Isostructural, Electronic band structure
Abstract: The synthesis, crystal structure, conductivity and electronic band structure of the new molecular metal α-(BEDT-TTF)2TlHg(se 1 -xSxCN) 4 (x = 0.125) are reported. α-(BEDT-TTF) 2 TlHg(Se 1-x S x CN) 4 (x = 0.125) is isostructural with all other members of the family of α-(BEDT-TTF) 2 MHg(XCN) 4 salts and is a stable metal down to very low temperatures. A general study of the electronic structure of all structurally characterized α-(BEDT-TTF) 2 M Hg(XCN) 4 salts as well as α-(BEDT-TTF) 2 I 3 , α-(BEDT-TTF) 2 IBr 2 and α-(BEDT-TTF) 4 PtBr 6 is also reported. Different aspects related to the electronic structure of these salts like the stability of the metallic state and the nature of the Fermi surface are discussed and correlated with the details of their crystal structures. The origin of the different dimensionality of the carriers for the α-(BEDT-TTF) 2 MHg(XCN) 4 salts (i.e., 1D electrons but 2D holes), the metal to insulator transition in α-(BEDT-TTF) 2 I 3 and the semiconducting behavior of α-(BEDT-TTF) 2 IBr 2 and α-(BEDT-TTF) 4 PtBr 6 are also discussed.
Published: 1996
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92. H2O photodissociation dynamics based on potential energy surfaces from density functional calculations

Author: G. J. Kroes, Marie-Liesse Doublet, A. Rosa, and E. J. Baerends
Subjects: Chemistry, Photodissociation, Ab initio, General Physics and Astronomy, Potential energy, Ab initio quantum chemistry methods, Excited state, Potential energy surface, Physics::Atomic and Molecular Clusters, Density functional theory, Physics::Chemical Physics, Physical and Theoretical Chemistry, Atomic physics, Ground state
Abstract: We investigate the usefulness of density functional theory (DFT) for calculating excited state potential energy surfaces. In the DFT calculations, the generalized gradient approximation (GGA) is used. As a test case, the photodissociation of H2O through the first excited A 1B1 state was considered. Two‐dimensional potential energy surfaces were obtained for both the X 1A1 ground state and the first excited state. Wave packet calculations employing these surfaces were used to obtain both the absorption spectrum and partial photodissociation cross sections, which are resolved with respect to the final vibrational state of the OH fragment. Comparisons are made with a previously calculated high level ab initio potential energy surface, with dynamics calculations using that surface, and with experiment. The vertical excitation energy for the (X 1A1→A 1B1) transition calculated using DFT is in good agreement with the previous ab initio calculations. The absorption spectrum and the partial cross sections obt...
Published: 1995
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93. Pseudocapacitive FeWO4 Electrode: From Charge Storage Mechanism to Practical Use in Asymmetric Cell

Author: Olivier Crosnier, Nicolas Goubard-Bretesché, Gaëtan Buvat, Camille Douard, Antonella Iadecola, Stéphanie Belin, Richard Retoux, Christophe Payen, Frederic Favier, Kazuaki Kisu, Etsuro Iwama, Katsuhiko Naoi, Marie-Liesse Doublet, and Thierry Brousse
Abstract: Pseudocapacitive electrodes can be of interest in order to improve the volumetric energy density of electrochemical capacitors, so called supercapacitors, owing to the high density of metal oxides or nitrides as compared to activated carbon [1]. Among all the materials that have been proposed up to now, iron tungstate (FeWO4) represents an interesting candidate both from a fundamental and application point of views. It crystallizes in the wolframite-type structure, characterized by distorted [MO6] and [WO6] octahedra. Different low-temperature methods including polyol-mediated synthesis [2], hydrothermal synthesis [3], ultracentrifugation method [4] have been used in order to obtain high specific surface area nanoparticles which have been characterized and electrochemically tested as supercapacitor electrode materials in aqueous electrolytes [5]. FeWO4 has demonstrated a pseudocapacitive behavior that can be attributed to Fe2+/Fe3+ surface redox reactions and thus is closely related to the specific surface area. To further investigate the charge-storage mechanism of FeWO4, in situ and operando X-ray absorption spectroscopy (XAS) experiments were performed at both Fe K- (7112 eV) and W L-edges (10204 and 12100 eV) on the new ROCK beamline at the SOLEIL synchrotron (France), using a specially designed 3-electrode-cell assembly. The composite working electrodes were composed of 60% FeWO4, 30% carbon black and 10% PTFE with a loading of about 10mg of FeWO4 per cm2. Cyclic voltammograms were obtained between -0.6 and 0 V vs. Ag/AgCl in neutral 5M LiNO3 at room temperature. An acquisition time of 100 ms per spectrum is possible on the ROCK beamline, thanks to its quick-EXAFS monochromator, thus allowing following very accurately the oxidation state evolution of both Fe and W in the electrodes during cycling. The XAS experiments show an evolution of the iron oxidation state (Fe2+/Fe3+) while cycling, thus confirming the Fe-related pseudocapacitive behavior of FeWO4, while no evolution was observed on the tungsten oxidation state. The characterizations and XAS results will be detailed in the presentation. Poor alteration of the crystal structure was also observed which open the way for the use of FeWO4 as possible long term cycling electrode in a supercapacitor. Thus, FeWO4 was tested as negative electrode in an asymmetric electrochemical capacitor using cryptomelane-type MnO2 as the positive in a neutral aqueous electrolyte. Prior to assembling the cell, the electrodes have been individually tested in a 5M LiNO3 electrolyte solution to define both the adequate balance of active material in the supercapacitor and the proper working voltage window. The full asymmetric device has been cycled between 0 and 1.4 V for over 40 000 cycles and subjected to accelerated ageing tests under floating conditions at different voltages, without any significant change on its electrochemical behavior. This remarkable stability shows the interest of developing full oxide-based asymmetric supercapacitors operating in non-toxic aqueous electrolytes. Cell performances will be reported in this communication. References 1) Nicolas Goubard-Bretesché, Olivier Crosnier, Gaëtan Buvat, Frédéric Favier, and Thierry Brousse, submitted to JPS, April 2016. 2) J. Ungelenk, M. Speldrich, R. Dronskowski, C. Feldmann, Solid State Sci. 31 (2014) 62. 3) S.H. Yu, B. Liu, M.S. Mo, J.H. Huang, X.M. Liu, Y.T. Qian, Adv. Funct. Mater. 13 (2003) 639. 4) K. Kisu, M. Iijima, E. Iwama, M. Saito, Y. Orikasa, W. Naoi and K. Naoi, J. Mater. Chem. A, 2014, 2, 13058-13068. 5) N. Goubard-Bretesché, O. Crosnier, C. Payen, F. Favier, T. Brousse, Electrochem. Commun. 57 (2015) 61.
Published: 2016
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94. Structural and electronic properties of the molecular conductors (EDTTTF)x[Pd(dmit)2]y(x:y=2:3 and 2:2)

Author: Enric Canadell, Luc Brossard, Patrick Cassoux, Marie-Liesse Doublet, J.-P. Legros, Jean-Paul Pouget, and B. Garreau
Subjects: Chemistry, Electron, Electronic structure, Condensed Matter Physics, Acceptor, Metal, Crystallography, Electrical resistivity and conductivity, visual_art, visual_art.visual_art_medium, Molecule, General Materials Science, Electronic band structure, Charge density wave
Abstract: Two new charge transfer salts combining the EDTTTF (ethylenedithiotetrathiafulvalene) donor and the Pd(dmit)2 acceptor (dmit2-=4, 5-dimercapto-1, 3-dithiole-2-thione) have been prepared and characterized. The molecular structure of the (EDTTTF)2(Pd(dmit)2)3 salt is quite unusual since the Pd(dmit)2 entities form true trimers through two strong interactions between the Pd atoms. These trimers of acceptors form slabs which alternate with slabs of (EDTTTF)2 pairs. Band structure calculations indicate a charge transfer of one electron per EDTTTF molecule and we expect this 2:3 salt to be a semiconductor. In the (EDTTTF)2[Pd(dmit)2]2 salt, the EDTTTF units form centrosymmetric pairs which pile up along (100) while the [Pd(dmit)2]2 dimers pile up along (101). Stacks of donors and acceptors form segregated slabs which alternate along (010). (EDTTTF)2[Pd(dmit)2]2 is metallic, and our studies suggest the occurrence of a charge transfer of 3/4 electrons per molecule. This salt exhibits a resistivity anomaly, a drop of spin susceptibility and a structural phase transition at 50 K. These data combined with electronic structure calculations show that this transition must be associated with a charge density wave (CDW) instabilty of the EDTTTF stacks. Finally we suggest that the resistivity anomaly of the related alpha -(EDTTTF)[Ni(dmit)2] salt is also due to a CDW instability of the donor slabs.
Published: 1995
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95. Effect of the cooling rate on the transverse magnetoresistance of (TSeT)2Cl in its charge-density wave ground state

Author: Alain Audouard, Enric Canadell, S. Askenazy, Rimma P. Shibaeva, Marie-Liesse Doublet, B. Hilti, V.N. Laukhin, Jean-Paul Pouget, J.P. Ulmet, F. Goze, Luc Brossard, V.E. Zavodnik, and C.W. Mayer
Subjects: Materials science, Condensed matter physics, Oscillation, Landau quantization, Condensed Matter::Mesoscopic Systems and Quantum Hall Effect, Condensed Matter Physics, Electronic, Optical and Magnetic Materials, Magnetic field, Cooling rate, Condensed Matter::Strongly Correlated Electrons, Electrical and Electronic Engineering, Ground state, Charge density wave, Transverse magnetoresistance
Abstract: Transverse magnetoresistance measurements were performed in pulsed magnetic fields up to 37 T in the metallic state and the semimetallic charge-density wave ground state of (TSeT) 2 Cl. Cooling with two different rates from 30 K down to 4.2 K yields two Shubnikov-de Haas oscillation frequencies. The 0 + Landau level is evidenced for both oscillation series.
Published: 1995
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96. A Fully Ordered Triplite, LiCuSO4f

Author: Meiling Sun, Gwenaelle Rousse, Daniel Dalla Corte, Matthieu Saubanere, Marie-Liesse Doublet, and Jean-Marie Tarascon
Abstract: Progresses on novel positive electrode materials of rechargeable Li-ion batteries showing safety, sustainability and cost advantages have been recently achieved with the arrival of polyanionic compounds. Pursuing chemical substitutions on the anionic sites our group has synthesized a triplite LiFeSO4F1,2 phase with a redox voltage of 3.9 V vs. Li+/Li0. Another way to modify the redox potential of polyanionic compounds consists in changing the nature of the 3d-metal. Recent DFT calculations have indicated that potentials as high as 5.1 V should be achievable for tavorite LiCuSO4F.3 This, combined with our recent finding of a 4.7 V redox activity in Li2CuO(SO4)2,4 was an impetus to further explore the Cu-based fluorosulfate chemistry which so far counts a sole member, the electrochemically inactive tavorite NaCuSO4F phase.5 Herein we report the synthesis, structure and physical properties of a newly synthesized LiCuSO4F phase. Interestingly, we show that this new compound crystallizes in a fully-ordered triplite structure with M1 being fully occupied with Cu and M2 with Li (Figure 2a). This is, to the best of our knowledge, the first experimental realization of triplite without any site mixing. This ordered triplite phase, whose stability was confirmed by DFT calculations, was characterized for its electrochemical properties. The Rietveld refinement of synchrotron and neutron diffraction patterns and the structure of LiCuSO4F is shown in Figure 1. The competitive formation of disordered or ordered triplite phase was evaluated through DFT calculations (Figure 2c). We demonstrate that both ordered CuM1 and CuM2 triplite LiCuSO4F polymorphs are thermodynamically equivalent, and more stable than either “tavorite” or “disordered triplite” polymorphs. The enthalpy governs the formation of an ordered LiCuSO4F triplite. This contrasts with the entropy-driven formation of LiFeSO4F disordered triplite in which all Fe-Li distributions are energetically equivalent. This new phase was tested for its electrochemical activity towards Li by assembling, in an argon dry box , LiCuSO4F/Li Swagelok-type cells using a 1M LiPF6 solution in 1:1:3 EC : PC : DMC electrolyte. The cells were charged to either 4.9 V or 5.2 V at different rates via a VMP system, but no sign of redox activity could be detected in the voltage composition curves. This means that no Li can be removed from this structure till 5.2V, the voltage at which we found the electrolyte copiously decomposes although DFT calculations shows the feasibility to stabilize an intermediate ordered Li0.5CuSO4F phase (Figure 2d). The electrochemical potentials computed for the two consecutive delithiation processes: LiCuSO4F – 0.5Li Li0.5CuSO4F and Li0.5CuSO4F – 0.5Li CuSO4F are 5.15 V and 5.40 V, respectively. This could not be confirmed experimentally owing to the lack of suitable electrolytes although we cannot eliminate kinetic issues associated to the poor Li ionic conductivity in LiCuSO4F (not shown here). Thus, the attractiveness of this new phase is limited application-wise. Nevertheless bearing in mind the richness of sulfate-/phosphate-based polyanionic electrodes adopting either the tavorite or disordered triplite structures, we believe that such a finding will contribute further in the understanding of these technologically important compounds. References (1) Ati, M.; Melot, B. C.; Rousse, G.; Chotard, J.-N.; Barpanda, P.; Tarascon, J.-M. Angewandte Chemie International Edition 2011, 50, 10574. (2) Barpanda, P.; Ati, M.; Melot, B. C.; Rousse, G.; Chotard, J. N.; Doublet, M. L.; Sougrati, M. T.; Corr, S. A.; Jumas, J. C.; Tarascon, J. M. Nat Mater 2011, 10, 772. (3) Mueller, T.; Hautier, G.; Jain, A.; Ceder, G. Chemistry of Materials 2011, 23, 3854. (4) Sun, M.; Rousse, G.; Abakumov, A. M.; Saubanère, M.; Doublet, M.-L.; Rodríguez-Carvajal, J.; Van Tendeloo, G.; Tarascon, J.-M. Chemistry of Materials 2015, 27, 3077. (5) Reynaud, M.; Barpanda, P.; Rousse, G.; Chotard, J.-N.; Melot, B. C.; Recham, N.; Tarascon, J.-M. Solid State Sciences 2012, 14, 15. Figure 1
Published: 2016
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97. An ab initio study of surface electrochemical disproportionation: The case of a water monolayer adsorbed on a Pd(1 1 1) surface

Author: Jean-Sébastien Filhol, Marie-Liesse Doublet, 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), 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), CINES under contract 1011750., 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: Chemistry, Ab initio, Disproportionation, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Pd(1 1 1) surface Disproportionation Electrochemistry Density functional theory Stability diagram Fukui function Orbital analysis Water monolayer, 01 natural sciences, Catalysis, 0104 chemical sciences, Metal, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Adsorption, Computational chemistry, Chemical physics, visual_art, Phase (matter), Monolayer, visual_art.visual_art_medium, Density functional theory, 0210 nano-technology, Fukui function
Abstract: International audience; We present a theoretical study of the structural response of model water monolayers on a Pd(1 1 1) surface upon various electrochemical conditions. Whereas the water molecules pointing toward the vacuum are mostly electrochemically inactive, those lying parallel to the surface undergo an oxidative adsorption under oxidizing conditions, and those pointing toward the surface show a reductive adsorption under reducing conditions. The oxidative adsorption is shown to result from the interaction of the H2O 1b1 orbital with the metal surface dz2 band which becomes bonding only under oxidative conditions. The reductive adsorption arises from the interaction of the H2O 4a1-2b2 orbitals with the dz2 band of the Pd surface. This electronic analysis of electrochemical effects is further validated using the Fukui function associated with the water monolayers. The Fukui function is shown to be a powerful tool for studying electrochemical effects as it is directly linked with the electrochemical bond reorganization and other parameters like the surface capacitance. The electrochemical stability diagram for these water monolayers is computed using a new correction for the DFT electrochemical calculations and compared to previous results. The phase transformation from a positively charge H-up to a negatively charged Hdown phase is here confirmed with, however, a potential shifted up to 4.5 V compared to our previous report (4.3 V). The neutral phase is found to consist in a positively charged H-up phase and a negatively charged H-down phase. This phenomenon is confirmed by large super-cell calculations with different ratio of H-up and H-down phases. The stability of the mixed charged phases is then rationalized in terms of an electrochemical disproportionation whose origin and consequences are further discussed in regards to the results previously obtained on the basis of the ice rules
Published: 2012
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98. ChemInform Abstract: Single-Step Synthesis of FeSO4F1-yOHy(0 ≤ y ≤ 1) Positive Electrodes for Li-Based Batteries

Author: Jean-Marie Tarascon, Gwenaëlle Rousse, Marie-Liesse Doublet, Moulay Tahar Sougrati, Nadir Recham, Jean-Claude Jumas, and M. Ati
Subjects: Chemical engineering, Chemistry, Electrode, Single step, General Medicine, Stoichiometry, Autoclave
Abstract: The title phases are synthesized from ball-milled, stoichiometric mixtures of FeF3 and Fe2(SO4)3·nH2O (autoclave, 300 °C, 50 h).
Published: 2012
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99. Single-Step Synthesis of FeSO4F1−yOHy (0 ≤ y ≤ 1) Positive Electrodes for Li-Based Batteries

Author: Gwenaëlle Rousse, Jean-Claude Jumas, M. Ati, Moulay Tahar Sougrati, Jean-Marie Tarascon, Marie-Liesse Doublet, Nadir Recham, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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), Institut de minéralogie et de physique des milieux condensés (IMPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-Université Paris Diderot - Paris 7 (UPD7)-Institut de Physique du Globe de Paris (IPG Paris)-Centre National de la Recherche Scientifique (CNRS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-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)-Institut de Chimie du CNRS (INC), and Université Pierre et Marie Curie - Paris 6 (UPMC)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, batteries, General Chemical Engineering, Inorganic chemistry, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Redox, Mössbauer spectroscopy, Materials Chemistry, fluorosulphate electrodes, chemistry.chemical_classification, Mössbauer effect, General Chemistry, Polymer, 021001 nanoscience & nanotechnology, 0104 chemical sciences, chemistry, hydroxyl-fluorosulfates, [PHYS.COND.CM-GEN]Physics [physics]/Condensed Matter [cond-mat]/Other [cond-mat.other], Electrode, X-ray crystallography, Physical chemistry, 0210 nano-technology, Solid solution
Abstract: International audience; The recent discovery of electrochemical activity at 3.6 V vs Li+/Li0 in LiFeSO4F has generated widespread research activity in this new family of fluorosulfate electrode materials aiming at either increasing the Fe3+/Fe2+ redox potential, searching for new active members, or extending this family to hydroxyl-fluorosulfates. Here we present a new low temperature single step synthesis of FeSO4F1−yOHy phases using FeF3 and Fe2(SO4)3*nH2O as precursors. Using thorough chemical analytical techniques to test for F− content in conjunction with Mössbauer measurements, we demonstrate the existence of a limited solid solution (0.35 < y
Published: 2012
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100. Application to trans-polyacetylene

Author: Christophe Iung, Enric Canadell, and Marie-Liesse Doublet
Subjects: Polyacetylene, chemistry.chemical_compound, Materials science, chemistry, Polymer chemistry
Published: 2012
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