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64 results on '"Marie-Liesse Doublet"'

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

Author

Thomas Marchandier, Sathiya Mariyappan, Artem M. Abakumov, Stéphane Jobic, Bernard Humbert, Jean-Yves Mevellec, Gwenaëlle Rousse, Maxim Avdeev, Rémi Dedryvère, Dominique Foix, Antonella Iadecola, Marie-Liesse Doublet, Jean-Marie Tarascon, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Skolkovo Institute of Science and Technology [Moscow] (Skoltech), Institut des Matériaux Jean Rouxel (IMN), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - Ecole Polytechnique de l'Université de Nantes (Nantes Univ - EPUN), Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université de Montpellier (UM), The University of Sydney, Australian Nuclear Science and Technology Organisation [Australie] (ANSTO), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Collège de France - Chaire Chimie du solide et énergie, Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), U.S. Department of Energy under contract no. DE-AC02-06CH11357European Research Council (ERC) (FP/2014)/ERC grant/project no. 670116-ARPEMA, ANR-10-EQPX-0045,ROCK,Spectromètre EXAFS Rapide pour Cinétiques Chimiques(2010), Chaire Chimie du solide et énergie, Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Fédérale Toulouse Midi-Pyrénées-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Sorbonne Université (SU)

Subjects
General Chemical Engineering, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Materials Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, [CHIM.OTHE]Chemical Sciences/Other, 010402 general chemistry, 021001 nanoscience & nanotechnology, 0210 nano-technology, 01 natural sciences, 0104 chemical sciences
Abstract

International audience; Li-ion batteries are growing in demand and such growth calls for the quest for high-energy-density electrode materials. Li-rich layered oxides that show both cationic and anionic redox are expected to meet the high energy requirement. However, the oxygen anion activity triggers numerous structural and electronic rearrangements that need to be understood prior to envisioning applications. Here, we chemically design two new LixIrS2 polymorphs to further interrogate the mechanisms of the ligand redox process. By combined structural and spectroscopic characterizations, we show that electrochemical lithiation/delithiation of the polymorphs involve different sulfur redox couples that stand as unusual behavior. These structure-dependent kinetic pathways lead to an similar to 1 V difference between the two polymorphs, hence providing the missing link between the structure and hysteresis in anionic redox systems. These insights into the origin of hysteresis can guide proper parameters to cure it, hence laying the groundwork for the design of new practical electrode materials.

Published
2021
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2. Stacking Versatility in Alkali-Mixed Honeycomb Layered NaKNi2TeO6

Author

Gwenaëlle Rousse, François Weill, François Fauth, Montse Casas-Cabanas, Jon Serrano-Sevillano, Marie-Liesse Doublet, Romain Berthelot, Bernard Fraisse, Dany Carlier, Danielle Laurencin, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), CIC ENERGIGUNE - Parque Tecnol Alava, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), CELLS ALBA, Barcelona 08290, Spain, Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Ikerbasque - Basque Foundation for Science, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), The BL04-MSPD staff of CELLS-ALBA synchrotron is acknowledged for granting beamtime through InHouse quota (proposal 2020014011)., Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Basque Foundation for Science (Ikerbasque)

Subjects
Diffraction, Chemistry, Sodium, Stacking, Honeycomb (geometry), Oxides, Context (language use), [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, Nuclear magnetic resonance spectroscopy, 010402 general chemistry, 021001 nanoscience & nanotechnology, Alkali metal, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Chemical physics, Cations, Potassium, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Density functional theory, Physical and Theoretical Chemistry, Layers, 0210 nano-technology, Stacking fault
Abstract

International audience; The reaction between P2-type honeycomb layered oxides Na2Ni2TeO6 and K2Ni2TeO6 enables the formation of NaKNi2TeO6. The compound is characterized by X-ray diffraction and 23Na solid-state nuclear magnetic resonance spectroscopy, and the structure is discussed through density functional theory calculations. In addition to the honeycomb Ni/Te cationic ordering, NaKNi2TeO6 exhibits a unique example of alternation of sodium and potassium layers instead of a random alkali-mixed occupancy. Stacking fault simulations underline the impact of the successive position of the Ni/Te honeycomb layers and validate the presence of multiple stacking sequences within the powder material, in proportions that evolve with the synthesis conditions. In a broader context, this work contributes to a better understanding of the alkali-mixed layered compounds.

Published
2021
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3. New p-type Al-substituted SrSnO3 perovskites for TCO applications?

Author

Rached Ben Hassen, Mouna Ben Yahia, Marie-Liesse Doublet, B. Belgacem, Leila Ben Amor, Jean-Sébastien Filhol, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Unité de Recherche de Chimie des Matériaux (ISSBAT), and Université de Tunis El Manar (UTM)

Subjects
010302 applied physics, Materials science, Metals and Alloys, chemistry.chemical_element, 02 engineering and technology, General Chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, Oxygen, Catalysis, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Crystallography, chemistry, 0103 physical sciences, Materials Chemistry, Ceramics and Composites, Valence band, [CHIM]Chemical Sciences, 0210 nano-technology
Abstract

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

Published
2020
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4. Investigation of alkali and alkaline earth solvation structures in tetraglyme solvent

Author

T. Picard, Jean-Sébastien Filhol, N. Sergent, Long H. B. Nguyen, Christophe Raynaud, Marie-Liesse Doublet, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Matériaux Interfaces ELectrochimie (MIEL), Laboratoire d'Electrochimie et de Physico-chimie des Matériaux et des Interfaces (LEPMI), Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Institut de Chimie du CNRS (INC)-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Materials science, Metal ions in aqueous solution, Implicit solvation, Solvation, General Physics and Astronomy, 02 engineering and technology, Electrolyte, 010402 general chemistry, 021001 nanoscience & nanotechnology, Alkali metal, 01 natural sciences, 0104 chemical sciences, Solvation shell, Chemical physics, Molecular vibration, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Molecule, Physical and Theoretical Chemistry, 0210 nano-technology
Abstract

International audience; This study compares molecular calculations performed with molecular and periodic codes through an investigation of the solvation structures of alkali and alkaline earth metal ions in tetraglyme solution. The two codes are able to produce equivalent structural and energetic information at the same level of theory, and in the presence of the implicit solvation model or not. This comparison reveals that molecular optimisations can be performed with periodic codes and used directly as input models for interface or electrochemistry calculations in order to preserve the solvent−solute interaction and the cavitation energy. By a rigorous comparison, we have demonstrated that equivalent energetic values can be obtained with the conventional PBE-D3 and the newly developed SCAN-rVV10 functional. Nevertheless, when the vibrational features are concerned and when the molecule possesses a highly conjugated system, the SCAN-rVV10 functional is required to describe the vibrational modes properly. The computed IR/Raman spectra can thus be used as essential information to determine the first solvation shell of metal ions in glyme-based solutions. In tetraglyme solution, the alkali and alkaline earth metal ions exhibit a diverse solvation structure. Small ions like Li+ and Mg2+ tend to adopt a coordination number of five or six, while larger ions, Na+, K+, and Ca2+, prefer an eight-coordinated environment, and the metal−ligand interaction increases in the order K+−O < Na+−O < Li+−O < Ca2+−O < Mg2+−O. The solvation spheres play a significant role in the stability and the reactivity of the solvated ions, and can thus be used as input models to construct the solvation structure in more sophisticated electrolytes, such as polyethylene oxide, or perform electrochemical calculations.

Published
2021
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5. Activation of anionic redox in d0 transition metal chalcogenides by anion doping

Author

Jean-Marie Tarascon, Artem M. Abakumov, Dominique Foix, Marie-Liesse Doublet, Elodie Salager, Rémi Dedryvère, Bernhard T. Leube, Hervé Vezin, Clara Robert, Gwenaëlle Rousse, Pierre-Etienne Cabelguen, Benjamin Porcheron, Université de Lille, CNRS, Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 [LASIRE], Collège de France (CdF (institution)), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement - UMR 8516 (LASIRE), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS), European Project: 670116,H2020,ERC-2014-ADG,ARPEMA(2015), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Institut de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL), and Laboratoire Avancé de Spectroscopie pour les Intéractions la Réactivité et l'Environnement (LASIRE) - UMR 8516

Subjects
inorganic chemicals, Materials science, Science, General Physics and Astronomy, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, 7. Clean energy, Redox, General Biochemistry, Genetics and Molecular Biology, Ion, Transition metal, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Twist, Multidisciplinary, Doping, Cationic polymerization, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Electron localization function, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Crystallography, [CHIM.POLY]Chemical Sciences/Polymers, 0210 nano-technology
Abstract

Expanding the chemical space for designing novel anionic redox materials from oxides to sulfides has enabled to better apprehend fundamental aspects dealing with cationic-anionic relative band positioning. Pursuing with chalcogenides, but deviating from cationic substitution, we here present another twist to our band positioning strategy that relies on mixed ligands with the synthesis of the Li2TiS3-xSex solid solution series. Through the series the electrochemical activity displays a bell shape variation that peaks at 260 mAh/g for the composition x = 0.6 with barely no capacity for the x = 0 and x = 3 end members. We show that this capacity results from cumulated anionic (Se2−/Sen−) and (S2−/Sn−) and cationic Ti3+/Ti4+ redox processes and provide evidence for a metal-ligand charge transfer by temperature-driven electron localization. Moreover, DFT calculations reveal that an anionic redox process cannot take place without the dynamic involvement of the transition metal electronic states. These insights can guide the rational synthesis of other Li-rich chalcogenides that are of interest for the development of solid-state batteries.

Published
2021
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6. Correlating ligand-to-metal charge transfer with voltage hysteresis in a Li-rich rock-salt compound exhibiting anionic redox

Author

Artem M. Abakumov, Rémi Dedryvère, Gwenaëlle Rousse, Jean-Marie Tarascon, Marie-Liesse Doublet, Moulay Tahar Sougrati, Anatoliy Senyshyn, Biao Li, Antonella Iadecola, Anatolii V. Morozov, Leiting Zhang, Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), and Collège de France (CdF (institution))

Subjects
General Chemical Engineering, Salt (chemistry), 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Redox, law.invention, Metal, law, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Lone pair, chemistry.chemical_classification, Chemistry, Ligand, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Cathode, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Hysteresis, [CHIM.POLY]Chemical Sciences/Polymers, Octahedron, Chemical physics, visual_art, visual_art.visual_art_medium, 0210 nano-technology
Abstract

Anionic redox is a double-edged sword for Li-ion cathodes because it offers a transformational increase in energy density that is also negated by several detrimental drawbacks to its practical implementation. Among them, voltage hysteresis is the most troublesome because its origin is still unclear and under debate. Herein, we tackle this issue by designing a prototypical Li-rich cation-disordered rock-salt compound Li1.17Ti0.33Fe0.5O2 that shows anionic redox activity and exceptionally large voltage hysteresis while exhibiting a partially reversible Fe migration between octahedral and tetrahedral sites. Through combined in situ and ex situ spectroscopic techniques, we demonstrate the existence of a non-equilibrium (adiabatic) redox pathway enlisting Fe3+/Fe4+ and O redox as opposed to the equilibrium (non-adiabatic) redox pathway involving sole O redox. We further show that the charge transfer from O(2p) lone pair states to Fe(3d) states involving sluggish structural distortion is responsible for voltage hysteresis. This study provides a general understanding of various voltage hysteresis signatures in the large family of Li-rich rock-salt compounds. The use of anionic redox chemistry in high-capacity Li-rich cathodes is being hampered by voltage hysteresis, the origin of which remains obscure. Now it has been shown that sluggish ligand-to-metal charge transfer kinetically traps an intermediate Fe4+ species and is responsible for voltage hysteresis in the prototypical Li-rich cation-disordered rock-salt Li1.17Ti0.33Fe0.5O2.

Published
2021
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7. Unlocking anionic redox activity in O3-type sodium 3d layered oxides via Li substitution

Author

Marie-Liesse Doublet, Anatolii V. Morozov, Benjamin Porcheron, Mohamed Chakir, Young-Sang Yu, Leiting Zhang, Artem M. Abakumov, Maxim Avdeev, Wanli Yang, Jordi Cabana, Sathiya Mariyappan, Jean-Marie Tarascon, Michaël Deschamps, Jinpeng Wu, Rémi Dedryvère, Gwenaëlle Rousse, Wang Qing, Collège de France (CdF (institution)), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Conditions Extrêmes et Matériaux : Haute Température et Irradiation (CEMHTI), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université d'Orléans (UO), Université d'Orléans (UO), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), ANR-10-EQPX-0045,ROCK,Spectromètre EXAFS Rapide pour Cinétiques Chimiques(2010), European Project: 670116,H2020,ERC-2014-ADG,ARPEMA(2015), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Université d'Orléans (UO)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), and Collège de France - Chaire Chimie du solide et énergie

Subjects
Materials science, Sodium, chemistry.chemical_element, 02 engineering and technology, Manganese, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Redox, Na-ion batteries, Affordable and Clean Energy, [CHIM.ANAL]Chemical Sciences/Analytical chemistry, Phase (matter), General Materials Science, Nanoscience & Nanotechnology, water-stable, Mechanical Engineering, cation migration, Cationic polymerization, General Chemistry, O3-type layered oxide, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, [CHIM.POLY]Chemical Sciences/Polymers, chemistry, Chemical engineering, Mechanics of Materials, Electrode, Density functional theory, 0210 nano-technology, anionic redox, Stoichiometry
Abstract

Sodium ion batteries, because of their sustainability attributes, could be an attractive alternative to Li-ion technology for specific applications. However, it remains challenging to design high energy density and moisture stable Na-based positive electrodes. Here, we report an O3-type NaLi1/3Mn2/3O2 phase showing anionic redox activity, obtained through a ceramic process by carefully adjusting synthesis conditions and stoichiometry. This phase shows a sustained reversible capacity of 190 mAh g−1 that is rooted in cumulative oxygen and manganese redox processes as deduced by combined spectroscopy techniques. Unlike many other anionic redox layered oxides so far reported, O3-NaLi1/3Mn2/3O2 electrodes do not show discernible voltage fade on cycling. This finding, rationalized by density functional theory, sheds light on the role of inter- versus intralayer 3d cationic migration in ruling voltage fade in anionic redox electrodes. Another practical asset of this material stems from its moisture stability, hence facilitating its handling and electrode processing. Overall, this work offers future directions towards designing highly performing sodium electrodes for advanced Na-ion batteries. Sodium ion batteries could be an attractive alternative to Li-ion technology but designing high energy density and moisture stable Na-based cathodes is challenging. Adjusting synthesis conditions and stoichiometry, an O3-type NaLi1/3Mn2/3O2 phase with anionic redox activity is reported.

Published
2021
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8. Unveiling Pseudocapacitive Charge Storage Behavior in FeWO 4 Electrode Material by Operando X‐Ray Absorption Spectroscopy

Author

Antonella Iadecola, Christophe Payen, Richard Retoux, Marie-Liesse Doublet, Etsuro Iwama, Katsuhiko Naoi, Frédéric Favier, Thierry Brousse, Nicolas Goubard-Bretesché, Camille Douard, Kazuaki Kisu, Olivier Crosnier, Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Laboratoire de cristallographie et sciences des matériaux (CRISMAT), Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Normandie Université (NU)-École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut de Recherche sur les Matériaux Avancés (IRMA), Normandie Université (NU)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Normandie Université (NU)-Institut national des sciences appliquées Rouen Normandie (INSA Rouen Normandie), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université de Rouen Normandie (UNIROUEN), Institut National des Sciences Appliquées (INSA)-Normandie Université (NU)-Institut National des Sciences Appliquées (INSA)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Tokyo University of Agriculture and Technology (TUAT), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), École Nationale Supérieure d'Ingénieurs de Caen (ENSICAEN), Normandie Université (NU)-Normandie Université (NU)-Centre National de la Recherche Scientifique (CNRS)-Université de Caen Normandie (UNICAEN), Normandie Université (NU)-Institut de Chimie du CNRS (INC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Pseudocapacitance 2, Absorption spectroscopy, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Redox, Pseudocapacitance, law.invention, Biomaterials, Metal, law, FeWO 4, General Materials Science, Operando, X-ray absorption spectroscopy, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Capacitor, Chemical physics, visual_art, Electrode, visual_art.visual_art_medium, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, Electrochemical capacitors, Biotechnology
Abstract

International audience; In nano-sized FeWO 4 electrode material, both Fe and W metal cations are suspected to be involved in the fast and reversible Faradaic surface reactions giving rise to its pseudocapacitive signature. As for any other pseudocapacitive materials, to fully understand the charge storage mechanism, a deeper insight into the involvement of the electroactive cations still has to be provided. The present paper illustrates how operando X-ray absorption spectroscopy (XAS) has been successfully used to collect data of unprecedented quality allowing to elucidate the complex electrochemical behavior of this multicationic pseudocapacitive material. Moreover, these in-depth experiments were obtained in real time upon cycling the electrode, which allowed investigating the reactions occurring in the material within a realistic timescale, which is compatible with electrochemical capacitors practical operation. Both Fe K-edge and W L 3-edge measurements point out the involvement of the Fe 3+ /Fe 2+ redox couple in the charge storage while W 6+ acts as a spectator cation. The result of this study enables to unambiguously discriminate between the Faradaic and capacitive behavior of FeWO 4. Beside these valuable insights toward the full description of the charge storage mechanism in FeWO 4 , this paper demonstrates the potential of operando X-ray absorption spectroscopy to enable a better material engineering for new high capacitance pseudocapacitive electrode materials.

Published
2020
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9. Unexpected band gap increase in the Fe2VAl Heusler compound

Author

Alexandre Berche, Philippe Jund, Marie-Liesse Doublet, Martin S. Talla Noutack, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Physics and Astronomy (miscellaneous), Band gap, FOS: Physical sciences, 02 engineering and technology, engineering.material, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Thermoelectric effect, Figure of merit, General Materials Science, thermally activated defects, Condensed Matter - Materials Science, Condensed matter physics, business.industry, thermoelectric materials, Materials Science (cond-mat.mtrl-sci), 021001 nanoscience & nanotechnology, Thermoelectric materials, Heusler compound, Semimetal, molecular dynamics, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Semiconductor, engineering, electronic properties, Density functional theory, Ab initio calculations, 0210 nano-technology, business, Heusler compounds, Energy (miscellaneous)
Abstract

Knowing the electronic structure of a material is essential in energy applications to rationalize its performance and propose alternatives. Materials for thermoelectric applications are generally small-gap semiconductors and should have a high figure of merit ZT. Even if the Fe2VAl Heusler compound has a decent ZT, its conductive nature (semi-metal or semiconductor) is not yet clarified especially at low temperature. In this paper, we focus our DFT calculations on the effect of temperature on the bandgap of Fe2VAl. In contrast to what is usually observed, we show that both the temperature increase and the formation of thermally-activated Al/V inversion defects (observed experimentally), open the bandgap. Such an unusual behavior is the key for reconciling all bandgap measurements performed on the Fe2VAl compound using a standard GGA functional and could be an efficient way for improving the thermoelectric properties of this family of materials., Comment: 10 pages, 5 figures

Published
2020
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10. The Structural Stability of P2-Layered Na-Based Electrodes during Anionic Redox

Author

Marie-Liesse Doublet, Jean Vergnet, Matthieu Saubanère, Jean-Marie Tarascon, Collège de France (CDF), Collège de France (CdF), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Chaire Chimie du solide et énergie, Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)

Subjects
Materials science, Stacking, Disproportionation, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Redox, Cathode, 0104 chemical sciences, law.invention, Hysteresis, General Energy, law, Structural stability, Chemical physics, Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Density functional theory, 0210 nano-technology, [CHIM.OTHE]Chemical Sciences/Other, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; The need to store an ever increasing amount of renewable energy in a sustainable way has rekindled interest for Na-ion batteries owing to the abundance of Na. Their energy density, lower than Li-Ion, can be enhanced by unlocking anionic redox, as recently reported in Na-deficient P2-phases. In contrast to their Li-rich counterparts with O3 stacking, these Na-deficient P2-phases show surprisingly good structural stability during anionic redox. Understanding the fundamental science at work in the relation between O/P stacking and anionic redox reversibility is critical to design stable anionic redox cathodes. Herein, through DFT-based analysis of the model compounds O2-and P2-Na2∕ 3Mg1∕3Mn2∕3O2, we show that the anionic redox process corresponds to a highly reversible collective distortion of the oxygen network in P stacking, or to a disproportionation of the oxygen pairs associated with significant voltage hysteresis in O stacking. Based on these findings, we used a magnetic-constrained DFT methodology to quantitatively predict the composition range of the reversible cycling that we successfully extend to other Mn-based cathodes (Na2∕ 3Zn1∕3Mn2∕3O2, Na 2 Mn 3 O 7). This article thus provides fundamental understanding, powerful computational methods and practical guidelines to design more stable anionic redox compounds.

Published
2020
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11. Thermodynamic origin of dendrite growth in metal anode batteries

Author

Marie-Liesse Doublet, Arthur Hagopian, Jean-Sébastien Filhol, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), and Centre National de la Recherche Scientifique (CNRS)

Subjects
Battery (electricity), Materials science, Renewable Energy, Sustainability and the Environment, 02 engineering and technology, Electrolyte, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Pollution, Capacitance, 0104 chemical sciences, Metal, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, Dendrite (crystal), Nuclear Energy and Engineering, Chemical physics, Whisker, visual_art, Electrode, visual_art.visual_art_medium, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Environmental Chemistry, 0210 nano-technology, Short circuit, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; The formation of dendrites in alkali and alkaline earth-metal batteries leads to short circuit and catastrophic battery failure which hinders the development of high-energy-density battery technology. Herein, we investigate the thermodynamic origin of this complex phenomenon and show that kinetic transport limitation of metal cations in the electrolyte is not the only factor controlling the formation of dendrites. The specific behavior of Li, Na and Mg electrodes towards dendritic growth is straightforwardly deduced from the shape of their electro-capillary diagrams, as computed from a grand canonical DFT approach. The whisker and dendrite morphologies associated with the different growth regimes are fully rationalized by the present methodology and the critical parameters controlling the dendritic growth on metallic surfaces are clearly identified. Further improving the description of the interface by means of a simplified yet realistic SEI built on carbonate-based decomposition products, we show that the over-potentials at which each growth regime is expected to occur can be predicted at a quantitative level, hence allowing the design of chemical strategies to prevent dendrite growth at metallic surfaces. More specifically, high surface tension associated with low surface capacitance and low potential of zero-charge is the target triptych to favor safe battery operation and can be obtained through appropriate chemical engineering.

Published
2020
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12. Atomic Structure of 2 nm Size Metallic Cobalt Prepared by Electrochemical Conversion: An in Situ Pair Distribution Function Study

Author

Damien Dambournet, Wei Li, Peter J. Chupas, Karena W. Chapman, Matthieu Saubanère, Marie-Liesse Doublet, Delphine Flahaut, Olaf J. Borkiewicz, PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), X-ray Science Division (XSD), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Argonne National Laboratory [Lemont] (ANL), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Diffraction, Atoms, Materials science, chemistry.chemical_element, Nanoparticle, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Metal, Physical and Theoretical Chemistry, Pair distribution function, Cobalt, Particle size, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, General Energy, chemistry, Chemical engineering, visual_art, Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], visual_art.visual_art_medium, 0210 nano-technology
Abstract

International audience; Conversion reactions, offering high capacity in batteries, imply a restructuration of the pristine atomic structure down to the nanoscale. The associated large broadening in the Bragg peaks of the restructured electrode renders the description of atomic structure, almost impossible using conventional X-ray diffraction. On the other hand, atomic pair distribution function (PDF) is well suited to probe the structure of few nanometer-sized particles. Here, we investigated the formation mechanism and structure of 2 nm particle size of metallic Co obtained by electrochemical conversion of CoF2. We found that the conversion process stabilized a disordered structure consisting of a hexagonal-close-pack-face-centered-pack intergrowth. The reaction was followed by in situ PDF, providing unique insight into the growth of highly defective Co nanoparticles.

Published
2018
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13. Requirements for reversible extra-capacity in Li-rich layered oxides for Li-ion batteries

Author

Ying Xie, Matthieu Saubanère, Marie-Liesse Doublet, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Key Laboratory of Functional Inorganic Material Chemistry, Ministry of Education, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Renewable Energy, Sustainability and the Environment, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Pollution, Oxygen, Redox, Reductive elimination, 0104 chemical sciences, Ion, Nuclear Energy and Engineering, chemistry, Chemical physics, Structural stability, Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Environmental Chemistry, Electron configuration, 0210 nano-technology
Abstract

International audience; The structural stability and the redox mechanism of Li-rich layered oxides (LLOs) are two very important aspectsfor high energy density. The former is related to the irreversible loss of lattice oxygen and capacity fading duringcycling, while the latter determines the overall capacity of the materials. This paper aims at clarifying the factorsgoverning the structural stability, the extra capacity and the redox mechanism of LLOs upon Li-removal. Theresults show that the structural stability against oxygen vacancy formation is improved with increasing M–Ocovalency, while it decreases with increasing d-shell electron number and with electrochemical extraction oflithium from the lattice. The redox mechanism of Li2-xMO 3 electrodes formed by 3d metals or by heavier metals0with a d electronic configuration is related to the electron depletion from the oxygen lone-pairs (localized non-bonding O(2p) states) leading to an irreversible anionic redox ending with the reductive elimination of O 2 uponcycling. For these phases, long-term cycling is predicted to be very unlikely due to the irreversible loss of latticenoxygen upon charging. For the electrodes formed by 4d and 5d metals with intermediate d electronicconfigurations, reversible cationic and anionic redox activities are predicted, therefore enabling reversible extra-capacities. The very different redox mechanisms exhibited by Li2-x MO3 electrodes are then linked to the delicatebalance between the Coulomb repulsions (U term) and the M–O bond covalency (D term) through the generaldescription of charge-transfer vs. Mott–Hubbard insulators. The present findings will provide a uniformguideline for tuning the band structures of Li2MO 3 phases and thus activating desired redox mechanisms,being beneficial for the design of high-energy density electrode materials for Li-ion battery applications

Published
2017
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14. Unified picture of anionic redox in Li/Na-ion batteries

Author

Matthieu Saubanère, Marie-Liesse Doublet, Mouna Ben Yahia, Jean Vergnet, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), École des Ponts ParisTech (ENPC), Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Centre National de la Recherche Scientifique (CNRS), and Collège de France (CdF)

Subjects
Materials science, Mechanical Engineering, Cationic polymerization, chemistry.chemical_element, Charge (physics), 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, Oxygen, Redox, Electron localization function, 0104 chemical sciences, chemistry, Transition metal, Mechanics of Materials, Chemical physics, Electrode, [CHIM]Chemical Sciences, General Materials Science, 0210 nano-technology, Lone pair
Abstract

International audience; Anionic redox in Li-rich and Na-rich transition metal oxides (A-rich-TMOs) has emerged as a new paradigm to increase the energy density of rechargeable batteries. Ever since, numerous electrodes delivering extra anionic capacity beyond the theoretical cationic capacity have been reported. Unfortunately, most often the anionic capacity achieved in charge is partly irreversible in discharge. A unified picture of anionic redox in A-rich-TMOs is designed here to identify the electronic origin of this irreversibility and to propose new directions to improve the cycling performance of the electrodes. The electron localization function is introduced as a holistic tool to unambiguously locate the oxygen lone pairs in the structure and follow their participation in the redox activity of A-rich-TMOs. The charge-transfer gap of transition metal oxides is proposed as the pertinent observable to quantify the amount of extra capacity achievable in charge and its reversibility in discharge, irrespective of the material chemical composition. From this generalized approach, we conclude that the reversibility of the anionic capacity is limited to a critical number of O holes per oxygen, hO ≤ 1/3.

Published
2019
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15. Zn 0.35 Co 0.65 O – A Stable and Highly Active Oxygen Evolution Catalyst Formed by Zinc Leaching and Tetrahedral Coordinated Cobalt in Wurtzite Structure

Author

Norbert Koch, Sayed M. El-Refaei, Ana Guilherme Buzanich, Sebastian Wahl, Marie-Liesse Doublet, Kug-Seung Lee, Nicola Pinna, Patrick Amsalem, Humboldt-Universität zu Berlin, BAM Bundesanstalt für Materialforschung u. -prüfung, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Humboldt University Of Berlin, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Materials science, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, Zinc, Overpotential, 010402 general chemistry, Electrochemistry, 01 natural sciences, 7. Clean energy, Catalysis, Structure-Property Relationships, General Materials Science, γ-Co(O)OH, Wurtzite crystal structure, Renewable Energy, Sustainability and the Environment, zinc, Oxygen evolution, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, cobalt, 0104 chemical sciences, chemistry, oxygen evolution reaction, Leaching (metallurgy), 0210 nano-technology, Cobalt, Wurtzite
Abstract

International audience; To arrive to sustainable hydrogen-based energy solutions, the understanding of water-splitting catalysts plays the most crucial role. Herein, we combined state-of-the-art hypotheses on electrocatalytic active metal sites towards the oxygen evolution reaction (OER) to develop a highly efficient catalyst based on earth-abundant cobalt and zinc oxides. The precursor catalyst Zn 0.35 Co 0.65 O was synthesized via a fast microwave-assisted approach at low temperatures. Subsequent, it transformed in situ from the Wurtzite structure to the layered γ-Co(O)OH, while most of its zinc leaches out. This material shows outstanding catalytic performance and stability towards the OER in 1 M KOH (overpotential at 10 mA cm-2 η initial = 306 mV, η 98 h = 318 mV). By comparing the electrochemical results and ex situ analyses to today's literature, we were able to identify clear structure-activity correlations. Our findings suggest that coordinately unsaturated cobalt octahedra on the surface are indeed the active centers for the OER.

Published
2019
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16. Evolution of Oxygen Ligands upon Large Redox Swings of Li3IrO4

Author

Jordi Cabana, Jean-Marie Tarascon, Marie-Liesse Doublet, Teak D. Boyko, Arnaud J. Perez, John W. Freeland, Beata Taudul, Haifeng Li, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Department of Chemistry, University of Illinois at Chicago, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Argonne National Laboratory [Lemont] (ANL), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Chaire Chimie du solide et énergie, University of Illinois [Chicago] (UIC), and University of Illinois System

Subjects
Materials science, Renewable Energy, Sustainability and the Environment, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Photochemistry, 01 natural sciences, Redox, Oxygen, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Materials Chemistry, Electrochemistry, [CHIM]Chemical Sciences, 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

International audience; The limits of intercalation electrochemistry continue to be tested in the quest for ever increasing gains in the storage capability of Li-ion cathodes. The subsequent push for multi-electron reactivity has led to the recognition of the extremely versatile role of oxide ligands in charge compensation when there is a large redox swing. Li 3 IrO 4 is a unique model of such activity because it can reversibly cycle between Li 1 IrO 4 and Li 4.7 IrO 4. Here, X-ray spectroscopy, magnetic measurements and computational simulations uncover the evolution of O states in the different steps, compared to the involvement of Ir. While the process between Li 1 IrO 4 and Li 3 IrO 4 is dominated by the unconventional lattice oxygen redox, the process between Li 3 IrO 4 and Li 4.7 IrO 4 involves a conventional change of the formal oxidation state of Ir, which affects O due to the high covalency. The O states of Li 3 IrO 4 exhibit a very high reversibility after the whole 3.7-electron process, completely restoring the pristine state.

Published
2021
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17. Elucidation of Active Oxygen Sites upon Delithiation of Li3IrO4

Author

Haifeng Li, Marie-Liesse Doublet, Jordi Cabana, Jean-Marie Tarascon, Arnaud J. Perez, Teak D. Boyko, John W. Freeland, Beata Taudul, Department of Chemistry, University of Liverpool, Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), Université de Strasbourg (UNISTRA)-Matériaux et nanosciences d'Alsace (FMNGE), Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS)-Réseau nanophotonique et optique, Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Centre National de la Recherche Scientifique (CNRS)-Université de Strasbourg (UNISTRA), Argonne National Laboratory [Lemont] (ANL), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), University of Illinois [Chicago] (UIC), and University of Illinois System

Subjects
Battery (electricity), Renewable Energy, Sustainability and the Environment, Chemistry, Inorganic chemistry, Oxide, Energy Engineering and Power Technology, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Cathode, 0104 chemical sciences, Redox Activity, law.invention, Active oxygen, chemistry.chemical_compound, Fuel Technology, Transition metal, Chemistry (miscellaneous), law, Materials Chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

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

Published
2021
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18. Chemical Activity of the Peroxide/Oxide Redox Couple: Case Study of Ba 5 Ru 2 O 11 in Aqueous and Organic Solvents

Author

Alexis Grimaud, John W. Freeland, Jean-Marie Tarascon, Antonella Iadecola, Haifeng Li, Matthieu Saubanère, Dmitry Batuk, Marie-Liesse Doublet, Jordi Cabana, Gwenaëlle Rousse, Artem M. Abakumov, Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Electron Microscopy for Materials Science - EMAT (Antwerp, Belgium), Universiteit Antwerpen = University of Antwerpen [Antwerpen], Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Argonne National Laboratory [Lemont] (ANL), University of Illinois [Chicago] (UIC), University of Illinois System, Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Chaire Chimie du solide et énergie, Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Universiteit Antwerpen [Antwerpen], Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
General Chemical Engineering, Oxide, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Photochemistry, Electrocatalyst, Electrochemistry, 01 natural sciences, 7. Clean energy, Peroxide, Redox, Oxygen, Article, chemistry.chemical_compound, Materials Chemistry, [CHIM]Chemical Sciences, ComputingMilieux_MISCELLANEOUS, Aqueous solution, Physics, Oxygen evolution, General Chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Chemistry, chemistry, 13. Climate action, 0210 nano-technology
Abstract

The finding that triggering the redox activity of oxygen ions within the lattice of transition metal oxides can boost the performances of materials used in energy storage and conversion devices such as Li-ion batteries or oxygen evolution electrocatalysts has recently spurred intensive and innovative research in the field of energy. While experimental and theoretical efforts have been critical in understanding the role of oxygen nonbonding states in the redox activity of oxygen ions, a clear picture of the redox chemistry of the oxygen species formed upon this oxidation process is still missing. This can be, in part, explained by the complexity in stabilizing and studying these species once electrochemically formed. In this work, we alleviate this difficulty by studying the phase Ba5Ru2O11, which contains peroxide O-2(2-) groups, as oxygen evolution reaction electrocatalyst and Li-ion battery material. Combining physical characterization and electrochemical measurements, we demonstrate that peroxide groups can easily be oxidized at relatively low potential, leading to the formation of gaseous dioxygen and to the instability of the oxide. Furthermore, we demonstrate that, owing to the stabilization at high energy of peroxide, the high-lying energy of the empty sigma* antibonding O-O states limits the reversibility of the electrochemical reactions when the O-2(2-)/O2- redox couple is used as redox center for Li-ion battery materials or as OER redox active sites. Overall, this work suggests that the formation of true peroxide O-2(2-) states are detrimental for transition metal oxides used as OER catalysts and Li-ion battery materials. Rather, oxygen species with O-O bond order lower than 1 would be preferred for these applications.

Published
2018
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19. The Electrochemical Sodiation of Sb Investigated by Operando X-ray Absorption and 121Sb Mössbauer Spectroscopy: What Does One Really Learn?

Author

Moulay Tahar Sougrati, Laure Monconduit, Raphaël P. Hermann, Marie-Liesse Doublet, Abdelfattah Mahmoud, Lorenzo Stievano, Bernard Fraisse, Mouna Ben Yahia, Ali Darwiche, Marcus Fehse, Camille La Fontaine, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), European Synchroton Radiation Facility [Grenoble] (ESRF), Delft University of Technology (TU Delft), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Group of Research in Energy and ENvironment from MATerials (GREENMAT), Université de Liège, Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Oak Ridge National Laboratory [Oak Ridge] (ORNL), UT-Battelle, LLC, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), European Project: 28721,ALISTORE, Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Dutch Belgian Beam line (DUBBLE), European Synchrotron Radiation Facility (ESRF), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Absorption spectroscopy, Analytical chemistry, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, DFT calculations, 01 natural sciences, Na-ion batteries, Antimony, Ab initio quantum chemistry methods, Phase (matter), Mössbauer spectroscopy, lcsh:TK1001-1841, Electrochemistry, Electrical and Electronic Engineering, Absorption (electromagnetic radiation), X-ray absorption spectroscopy, [CHIM.MATE]Chemical Sciences/Material chemistry, alloy reaction, 021001 nanoscience & nanotechnology, chemometrics, 3. Good health, 0104 chemical sciences, Amorphous solid, lcsh:Production of electric energy or power. Powerplants. Central stations, MCR-ALS, chemistry, lcsh:Industrial electrochemistry, 0210 nano-technology, Sb, lcsh:TP250-261
Abstract

In this study, we want to highlight the assets and restrictions of X-ray absorption spectroscopy (XAS) and M&ouml, ssbauer spectroscopy for investigating the mechanism of the electrochemical reaction of antimony electrode materials vs. Na. For this, operando XAS was carried out during the first one and a half cycles, and the whole set of measured data was analysed using a statistical-chemometric approach, while low temperature M&ouml, ssbauer spectroscopy measurements were carried out ex situ on selected samples stopped at different points of the electrochemical reaction. Complementary ab initio calculations were performed to support the experimental findings. Both techniques show that, upon the first sodiation, most Sb reacts with Na to form disordered Na 3 Sb. This step is accompanied by the formation of amorphous Sb as an intermediate. Upon inversion of the current Na 3 Sb is desodiated and an amorphous Sb phase, distinct from the pristine bulk Sb state, is gradually formed. However, both XAS and M&ouml, ssbauer spectroscopy were unable to spot the formation of intermediate Na x Sb phases, which were evinced in previous works by operando Pair Distribution Function analyses. The results shown here clearly assign such failure to the intrinsic inability of both techniques to identify these intermediates.

Published
2018
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20. A chemical approach to raise cell voltage and suppress phase transition in O3 sodium layered oxide electrodes

Author

Jean-Marie Tarascon, Joke Hadermann, Quentin Jacquet, Mariyappan Sathiya, Olesia M. Karakulina, Marie-Liesse Doublet, Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Sorbonne Université (SU), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Electron Microscopy for Materials Science - EMAT (Antwerp, Belgium), Universiteit Antwerpen [Antwerpen], Collège de France - Chaire Chimie du solide et énergie, Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), and Universiteit Antwerpen = University of Antwerpen [Antwerpen]

Subjects
Phase transition, Materials science, Oxide, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 7. Clean energy, 01 natural sciences, Redox, Metal, chemistry.chemical_compound, Transition metal, Phase (matter), [CHIM]Chemical Sciences, General Materials Science, Renewable Energy, Sustainability and the Environment, Physics, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Chemistry, Chemical engineering, chemistry, visual_art, Electrode, visual_art.visual_art_medium, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, Engineering sciences. Technology
Abstract

International audience; Sodium ion batteries (NIBs) are one of the versatile technologies for low‐cost rechargeable batteries. O3‐type layered sodium transition metal oxides (NaMO2, M = transition metal ions) are one of the most promising positive electrode materials considering their capacity. However, the use of O3 phases is limited due to their low redox voltage and associated multiple phase transitions which are detrimental for long cycling. Herein, a simple strategy is proposed to successfully combat these issues. It consists of the introduction of a larger, nontransition metal ion Sn4+ in NaMO2 to prepare a series of NaNi0.5Mn0.5− y Sn y O2 (y = 0–0.5) compositions with attractive electrochemical performances, namely for y = 0.5, which shows a single‐phase transition from O3 ⇔ P3 at the very end of the oxidation process. Na‐ion NaNi0.5Sn0.5O2/C coin cells are shown to deliver an average cell voltage of 3.1 V with an excellent capacity retention as compared to an average stepwise voltage of ≈2.8 V and limited capacity retention for the pure NaNi0.5Mn0.5O2 phase. This study potentially shows the way to manipulate the O3 NaMO2 for facilitating their practical use in NIBs.

Published
2018
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21. Competition between Metal Dissolution and Gas Release in Li-Rich Li 3 Ru y Ir 1– y O 4 Model Compounds Showing Anionic Redox

Author

Quentin Jacquet, Gwenaëlle Rousse, Matthieu Saubanère, Antonella Iadecola, Jean-Marie Tarascon, Erik J. Berg, Marie-Liesse Doublet, Daniel Alves Dalla Corte, Louis Lemarquis, Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Paul Scherrer Institute (PSI), Chaire Chimie du solide et énergie, Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, Absorption spectroscopy, 020209 energy, General Chemical Engineering, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, Mass spectrometry, Redox, Ultraviolet visible spectroscopy, Chemical engineering, 0202 electrical engineering, electronic engineering, information engineering, Materials Chemistry, Degradation (geology), [CHIM]Chemical Sciences, Density functional theory, 0210 nano-technology, Dissolution
Abstract

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.8b02955. Crystallographic data, additional Rietveld refinements, and EXAFS analysis (PDF) PDF cm8b02955_si_001.pdf (1.91 MB); International audience; Li-ion batteries have experienced tremendous progress over the past decade; however, their energy density should still be increased to power electric vehicles. Following this aim, the energy density of the cathode material can be drastically increased by making use of anionic redox, although it often comes along with material degradation. In this study, through a detailed analysis of the charge compensation mechanism of Li3RuO4 by online electrochemical mass spectrometry, X-ray absorption spectroscopy, and ultraviolet spectroscopy, we unveiled a new degradation mechanism for a cathode material showing anionic redox, namely the dissolution of Ru forming RuO4/RuO4– species with limited release of gas from the material. We show that this dissolution can be effectively tackled by substituting Ru with Ir. However, such a strategy leads to a massive increase in the release of O2 gas at the end of the charge. Density functional theory calculations prove that the relative stability of the end members RuO4 and IrO4 versus oxygen release is at the origin of this competition between metal dissolution and gas release.

Published
2018
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22. Electrochemical Mg alloying properties along the Sb1-xBix solid solution

Author

Danielle Laurencin, Fabrizio Murgia, Marie-Liesse Doublet, Romain Berthelot, Ephrem Terefe Weldekidan, Lorenzo Stievano, Laure Monconduit, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), PEPS CNRS 2014 Alabama and 2015 SurfMag, ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), and Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Diffraction, Materials science, General Chemical Engineering, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 25Mg solid-state NMR, DFT calculations, 01 natural sciences, Bismuth, Ball milling, Antimony, [CHIM]Chemical Sciences, Nuclear magnetic resonance spectroscopy, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Operando XRD, 0104 chemical sciences, Mg-battery, chemistry, Electrode, Density functional theory, 0210 nano-technology, Solid solution
Abstract

International audience; Despite strong physical and chemical similarities between antimony and bismuth, a distinct behaviour is observed in the electrochemical magnesiation of their micrometric powders. Bismuth undergoes a complete and highly reversible alloying reaction, whereas antimony displays no electrochemical activity. Taking advantage of the complete SbBi solid solution, monophasic compositions Sb1-xBix were prepared by high-energy mechanochemical synthesis and characterized by X-ray diffraction and solid-state 25Mg nuclear magnetic resonance spectroscopy. The electrochemical magnesiation at low current rate shows a full alloying process of Sb1-xBix-based electrodes leading to monophasic Mg3(Sb1-xBix)2. This chemical association of antimony and bismuth enables a positive effect on the electrochemical magnesiation of the electrode and enables higher specific capacities compared to Bi-based electrodes. However, this synergy only operates in the nominal discharge since an irreversible capacity loss, which scales with the antimony content, is observed in the subsequent charge. Operando XRD reveals a complex segregation process leading to pure bismuth and Mg3Sb2 at the end of charge which is further rationalized by density functional theory calculations as an instability of the Mg3(Sb1-xBix)2 solid solution.

Published
2018
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23. Electrostatic interactions vs. second order Jahn-Teller distortion as the source of structural diversity in Li 3 MO 4 compounds (M = Ru, Nb, Sb and Ta)

Author

Gwenaëlle Rousse, Quentin Jacquet, Matthieu Saubanère, Jean-Marie Tarascon, Marie-Liesse Doublet, Antonella Iadecola, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Chaire Chimie du solide et énergie, Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Institut de minéralogie et de physique des milieux condensés (IMPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Synchrotron SOLEIL (SSOLEIL), Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, and Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)

Subjects
Diffraction, Materials science, Absorption spectroscopy, General Chemical Engineering, Jahn–Teller effect, Cationic polymerization, Structural diversity, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrostatics, 01 natural sciences, 0104 chemical sciences, Crystallography, Order (biology), Materials Chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, Superstructure (condensed matter), ComputingMilieux_MISCELLANEOUS
Abstract

International audience; With the advent of layered rocksalt oxides showing anionic redox activity toward Li, there has been an increased focus on designing new rocksalt structures and, more particularly, compounds pertaining to the Li3MO4 family. The structural richness of this family is nested in its ability to host many different cations, leading to the formation of superstructure patterns whose predictability is still limited. Thus, there is a need to understand the formation of such superstructures, as cationic arrangements have a crucial effect on their physical properties. Herein we propose a combined experimental and theoretical approach to understand the interactions governing cation ordering in binary systems of general composition given by Li3MyM′1–yO4 (M and M′ being Ru, Nb, Sb, and Ta). Through complementary X-ray diffraction and X-ray absorption spectroscopy techniques, we reveal a solid-solution behavior for the Li3RuySb1–yO4 system, as opposed to Li3SbyNb1–yO4 that enlists four rocksalt structures with different cation orderings. We use DFT calculations to rationalize such a structural diversity and find that it is controlled by a delicate balance between electrostatic interactions and charge transfer due to a second order Jahn–Teller distortion. This insight provides a new viewpoint for understanding cationic arrangements in rocksalt structures and guidelines to design novel phases for applications such as Li-ion batteries or ionic conductors.

Published
2018
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24. The electrochemical activity of the nitrosyl ligand in copper nitroprusside: a new possible redox mechanism for lithium battery electrode materials?

Author

Moulay Tahar Sougrati, Marco Giorgetti, Marie-Liesse Doublet, Lorenzo Stievano, Angelo Mullaliu, Giuliana Aquilanti, Nicolas Louvain, Alma Mater Studiorum Università di Bologna [Bologna] (UNIBO), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Chimie, Ingénierie Moléculaire et Matériaux d'Angers (CIMMA), Université d'Angers (UA)-Centre National de la Recherche Scientifique (CNRS), Elettra Sincrotrone Trieste, Mullaliu, A., Sougrati, M. -. T. b, Louvain, N. b, Aquilanti, G., Doublet, M. -. L., Stievano, L., Giorgetti, M., Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Nitrosyl group, Chemistry, Ligand, General Chemical Engineering, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, Prussian blue analog, [CHIM.MATE]Chemical Sciences/Material chemistry, Operando characterization, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Redox, Copper, Lithium battery, 0104 chemical sciences, X-ray absorption fine structure, Lithium, Fourier transform infrared spectroscopy, 0210 nano-technology, Reduction mechanism
Abstract

International audience; The unconventional redox mechanism of copper nitroprusside in the electrochemical reaction with lithium is studied by a wide range of techniques. After a simple and reproducible synthesis, pristine copper nitroprusside is characterized using a wide range of techniques. The material is formulated and electrochemically tested in coin cells to explore its electrochemical signature and cyclability. Multiple redox processes involving both Fe and Cu centres are identified at an early stage and further investigated by operando XAFS. Moreover, operando FTIR unveils the unexpected participation of the nitrosyl ligand in the electrochemical reaction. A gradual and irreversible transformation of the material, also reported by operando Mössbauer spectroscopy, occurs in the first cycles. Then, the material is able to withstand several electrochemical cycles without efficiency loss, even though no optimization on formulation has been carried out. Altogether, the nitrosyl group is electrochemically active beyond metals’ centres, giving as result a remarkable increase in capacity compared to other analogue compounds. We thus believe this study may open the way to further research on other electroactive nitrosyl-containing materials.

Published
2017
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25. Evidence for anionic redox activity in a tridimensional-ordered Li-rich positive electrode β-Li2IrO3

Author

Artem M. Abakumov, Dominique Foix, Arnaud J. Perez, Gustaaf Van Tendeloo, Marie-Liesse Doublet, Paul E. Pearce, Jean-Marie Tarascon, Dmitry Batuk, Mathieu Saubanère, Gwenaëlle Rousse, Eric McCalla, Chimie du solide et de l'énergie (CSE), Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), University of Antwerp (UA), Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux (IPREM), Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), University of Minnesota [Twin Cities] (UMN), University of Minnesota System, Skolkovo Institute of Science and Technology [Moscow] (Skoltech), Chaire Chimie du solide et énergie, Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Université Pierre et Marie Curie - Paris 6 (UPMC), and EMAT University of Antwerp - Groenenborgerlaan 171, B-2020 Antwerp, Belgique

Subjects
Solid-state chemistry, Inorganic chemistry, Neutron diffraction, 02 engineering and technology, 010402 general chemistry, Electrochemistry, 01 natural sciences, Redox, Solid state chemistry, Batteries, [CHIM]Chemical Sciences, General Materials Science, Batteries, Solid state chemistry, Chemistry, Physics, Mechanical Engineering, Cationic polymerization, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Crystallography, Mechanics of Materials, Transmission electron microscopy, Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Density functional theory, [CHIM.OTHE]Chemical Sciences/Other, 0210 nano-technology
Abstract

International audience; Lithium-ion battery cathode materials have relied on cationic redox reactions until the recent discovery of anionic redox activity in Li-rich layered compounds which enables capacities as high as 300 mAh g-1. In the quest for new high-capacity electrodes with anionic redox, a still unanswered question was remaining regarding the importance of the structural dimensionality. The present manuscript provides an answer. We herein report on a β-Li2IrO3 phase which, in spite of having the Ir arranged in a tridimensional (3D) framework instead of the typical two-dimensional (2D) layers seen in other Li-rich oxides, can reversibly exchange 2.5 e- per Ir, the highest value ever reported for any insertion reaction involving d-metals. We show that such a large activity results from joint reversible cationic (Mn+) and anionic (O2)n- redox processes, the latter being visualized via complementary transmission electron microscopy and neutron diffraction experiments, and confirmed by density functional theory calculations. Moreover, β-Li2IrO3 presents a good cycling behaviour while showing neither cationic migration nor shearing of atomic layers as seen in 2D-layered Li-rich materials. Remarkably, the anionic redox process occurs jointly with the oxidation of Ir4+ at potentials as low as 3.4 V versus Li+/Li0, as equivalently observed in the layered α-Li2IrO3 polymorph. Theoretical calculations elucidate the electrochemical similarities and differences of the 3D versus 2D polymorphs in terms of structural, electronic and mechanical descriptors. Our findings free the structural dimensionality constraint and broaden the possibilities in designing high-energy-density electrodes for the next generation of Li-ion batteries.

Published
2017
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26. An Oxysulfate Fe2O(SO4)2 Electrode for Sustainable Li-Based Batteries

Author

Marie-Liesse Doublet, Moulay Tahar Sougrati, Artem M. Abakumov, Matthieu Courty, Gwenaëlle Rousse, Gustaaf Van Tendeloo, Meiling Sun, Jean-Marie Tarascon, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Université Pierre et Marie Curie - Paris 6 (UPMC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), RS2E, Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Chaire Chimie du solide et énergie, and Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)

Subjects
Electrode material, Chemistry, Inorganic chemistry, Nanotechnology, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Biochemistry, Redox, Catalysis, 0104 chemical sciences, Colloid and Surface Chemistry, Octahedron, Phase (matter), Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology
Abstract

International audience; High-performing Fe-based electrodes for Li-based batteries are eagerly pursued because of the abundance and environmental benignity of iron, with especially great interest in polyanionic compounds because of their flexibility in tuning the Fe3+/Fe2+ redox potential. We report herein the synthesis and structure of a new Fe-based oxysulfate phase, Fe2O(SO4)2, made at low temperature from abundant elements, which electrochemically reacts with nearly 1.6 Li atoms at an average voltage of 3.0 V versus Li+/Li, leading to a sustained reversible capacity of ≈125 mAh/g. The Li insertion–deinsertion process, the first ever reported in any oxysulfate, entails complex phase transformations associated with the position of iron within the FeO6 octahedra. This finding opens a new path worth exploring in the quest for new positive electrode materials.

Published
2014
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27. 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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28. 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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29. 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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30. 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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31. 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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32. 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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33. 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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34. 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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35. 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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36. 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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37. 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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38. 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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39. 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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40. 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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41. 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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42. 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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43. 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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44. 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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45. Origin of the 3.6V to 3.9V voltage increase in the LiFeSO4F cathodes for Li-Ion Batteries

Author

Gwenaëlle Rousse, Mouna Ben Yahia, Marie-Liesse Doublet, Frédéric Lemoigno, Florent Boucher, Jean-Marie Tarascon, 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), 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 des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), RS2E, Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Université Pierre et Marie Curie - Paris 6 (UPMC)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), and Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Renewable Energy, Sustainability and the Environment, Chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Pollution, Cathode, 0104 chemical sciences, law.invention, Ion, Crystallography, Nuclear Energy and Engineering, Transition metal, Octahedron, Cathode material, law, Fluorine, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Environmental Chemistry, 0210 nano-technology, High potential, Voltage
Abstract

International audience; Recently, the LiFeSO4F material has been reported as the highest potential Fe-based cathode material for Li-Ion batteries. Its working voltage vs. Li+/Li0 jumps from 3.6 V to 3.9 V when LiFeSO4F is synthesized in the fully ordered tavorite structure and in the fully disordered triplite structure, respectively. The present study aims at rationalizing this voltage increase by means of DFT+U calculations combined with crystallographic and electrostatic analyses. We show that the triplite polymorph, although characterized by two distinct edge-shared crystallographic sites, locally exhibits corner-sharing connections between consecutive FeO4F2 octahedra, exactly as in the tavorite polymorph. As a consequence, edge-sharing connections exist in the lithiated triplite structure between consecutive FeO4F2 and LiO4F2 polyhedra. We then demonstrate that the origin of the voltage increase lies in the difference in the anionic networks of the two polymorphs, and more specifically in the electrostatic repulsions induced by the configuration of the fluorine atoms around the transition metal in the two polymorphs (trans- vs. cis-configuration in tavorite vs. triplite). Such a finding should help in the design of novel high potential fluorosulphate materials, which beyond enhanced performances present sustainability attributes as they can be made from abundant elements and via low temperature eco-efficient process.

Published
2012
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46. Comparison of the electronic structures of isostructural (BEDT-TTF)3(HSO4)2 and [ Ni(dddt)2] 3(HSO4)2 molecular metals

Author

Enric Canadell, Rimma P. Shibaeva, Marie-Liesse Doublet, and Jean-Paul Pouget

Subjects
Materials science, General Engineering, Statistical and Nonlinear Physics, Insulator (electricity), Fermi surface, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Metal, Crystallography, Diffuse scattering, [PHYS.HIST]Physics [physics]/Physics archives, visual_art, visual_art.visual_art_medium, Isostructural, 0210 nano-technology, Electronic band structure, Closed loop
Abstract

The isostructural charge transfer salts (BEDT-TTF)3(HSO4)2 and [ Ni(dddt)2] 3(HSO4)2 are metallic at room temperature and exhibit metal to insulator transitions at 130 K and 25 K, respectively. X-ray diffuse scattering measurements for (BEDT-TTF)3(HSO4)2 and tight-binding band structure calculations for both salts suggest that these transitions are most likely due to slight structural modifications, probably donor displacements, which suppress the semi-metallic overlap in these 3:2 salts. Although the Fermi surface of (BEDT-TTF)3(HSO4)2 is made of closed loops, our study suggests that this salt has remarkable pseudo-1D properties. We show that even when they are isostructural, the BEDT-TTF and Ni(dddt)2 salts can be electronically quite different, because the LUMO of the latter donor is not too far in energy from the HOMO. Consequently, the LUMO of Ni(dddt)2 can mix into the partially filled bands of their charge transfer salts, which are based on the HOMO of the donor. This feature can change noticeably the topology of the band structure and the Fermi surface. We show that this actually happens in [ Ni(dddt)2] 3(HSO4)2 and that it can be the clue to understand the differences in physical properties of the (BEDT-TTF)2(HSO4)2 and [ Ni(dddt)2] 3(HSO4), salts.

Published
1994
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47. FeII/FeIII mixed-valence state induced by Li-insertion into the metal-organic-framework Mil53(Fe): A DFT+U study

Author

M. Ben Yahia, C. Combelles, Marie-Liesse Doublet, Laurent Pedesseau, 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), ANR-06-BLAN-0202,CONDMOFs,Preparation and characterization of lithium-inserted iron(i,iI) nanoporous hybrid solids(2006), 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
Valence (chemistry), Renewable Energy, Sustainability and the Environment, Chemistry, Inorganic chemistry, Energy Engineering and Power Technology, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Redox, Cathode, 0104 chemical sciences, Ion, law.invention, law, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Antiferromagnetism, Physical chemistry, Metal-organic framework, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, 0210 nano-technology, Porosity, Lithium-ion batteries First-principles DFT calculations Redox mechanisms Mixedvalence State
Abstract

International audience; The iron-based metal-organic-framework MIL53(Fe) has recently been tested as a cathode materials for Li-Ion batteries, leading to promising cycling life and rate capability. Despite a poor capacity of 70mAhg−1 associated with the exchange of almost 0.5Li/Fe, this result is the first evidence of a reversible lithium insertion never observed in a MOF system. In the present study, the MIL53(Fe) redox mechanism is investigated through first-principles DFT+U calculations. The results show that MIL53(Fe) is a weak antiferromagnetic charge transfer insulator at T = 0K, with iron ions in the high-spin S = 5/2 state. Its reactivity vs elemental lithium is then investigated as a function of lithium composition and distribution over the most probable Li-sites of theMOFstructure. The redox mechanism is fully interpreted as a two-step insertion/ conversion mechanism, associated with the stabilization of the Fe3+/Fe2+ mixed-valence state prior to the complete decomposition of the inorganic-organic interactions within the porousMOFarchitecture.

Published
2011
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48. Interface Electrochemistry in Conversion Reactions for Li-Ion Batteries

Author

Marie-Liesse Doublet, Anne-Laure Dalverny, Jean-Sébastien Filhol, 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), 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
Work (thermodynamics), Chemistry, Superlattice, Analytical chemistry, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Redox, 0104 chemical sciences, Ion, Hysteresis, Chemical physics, Electrode, Materials Chemistry, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology, Voltage
Abstract

International audience; This work presents a new methodology based on a multi-interface superlattice approach to investigate interface electrochemistry in conversion reactions, through first-principles DFT or DFT+U calculations. This method is applied to the CoO electrode for which several experimental data are available, and describes the main interface effects by means of three interdependent descriptors, namely the chemical (interface bonding), the mechanical (stress) and the electrical/electrochemical (electric bias) descriptors. Thanks to this decomposition, the most probable interfaces occurring during the CoO conversion have been determined, and a probable electrode morphology has been proposed. Furthermore, the addition of an external redox potential to the multi-interface superlattice has revealed asymmetric electrochemical interface phenomena in charge and discharge, shedding some lights into the voltage hysteresis observed for the CoO conversion/reconversion.

Published
2011
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49. A 3.90V iron-based fluorosulphate material for lithium-ion batteries crystallizing in the triplite structure

Author

Jean-Noël Chotard, Brent C. Melot, Prabeer Barpanda, Jean-Marie Tarascon, Jean-Claude Jumas, Marie-Liesse Doublet, Serena A. Corr, M. Ati, Moulay Tahar Sougrati, Gwenaëlle Rousse, 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 de minéralogie et de physique des milieux condensés (IMPMC), Université Pierre et Marie Curie - Paris 6 (UPMC)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Centre National de la Recherche Scientifique (CNRS), 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), School of Physical Sciences [Canterbury], University of Kent [Canterbury], Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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 Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), and 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)

Subjects
Materials science, Mechanical Engineering, chemistry.chemical_element, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, 7. Clean energy, Redox, Energy storage, 0104 chemical sciences, Ion, chemistry, Chemical engineering, Mechanics of Materials, Iron based, Energy density, Forensic engineering, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], General Materials Science, Lithium, Electronics, 0210 nano-technology
Abstract

International audience; Li-ion batteries have empowered consumer electronics and are now seen as the best choice to propel forward the development of eco-friendly (hybrid) electric vehicles. To enhance the energy density, an intensive search has been made for newpolyanionic compounds that have a higher potential for the Fe2C=Fe3C redox couple. Herein we push this potential to 3.90V in a new polyanionic material that crystallizes in the triplite structure by substituting as little as 5 atomic per cent of Mn for Fe in Li(Fe1 Mn )SO4F. Not only is this the highest voltage reported so far for the Fe2C=Fe3C redox couple, exceeding that of LiFePO4 by 450mV, but this new triplite phase is capable of reversibly releasing and reinserting 0.7-0.8 Li ions with a volume change of 0.6% (compared with 7 and 10% for LiFePO4 and LiFeSO4F respectively), to give a capacity of 125mAh g1.

Published
2011
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50. Design of Electrode Materials for Lithium-Ion Batteries: The Example of Metal-Organic Frameworks

Author

M. Ben Yahia, Laurent Pedesseau, C. Combelles, 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), ANR-06-BLAN-0202,CONDMOFs,Preparation and characterization of lithium-inserted iron(i,iI) nanoporous hybrid solids(2006), 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
Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 7. Clean energy, 01 natural sciences, Redox, Energy storage, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, General Energy, Chemical bond, chemistry, Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], Lithium, Metal-organic framework, Reactivity (chemistry), Li-Ion batteries First-Princples DFT+U calculations Metal Organic Framework, Physical and Theoretical Chemistry, 0210 nano-technology
Abstract

International audience; In the field of energy storage and Li-ion batteries, searching for new (positive) electrode materials with better electrochemical performances than those of transition-metal oxides is of permanent concern. To that aim, very simple concepts of chemical bonding can be used to find out the origin of the electrode limitations and to guide experimentalists for the design of new promising materials. This local approach was recently applied to hybrid architectures, such as metal-organic frameworks (MOFs), and allowed some of us to demonstrate the first reversible lithium insertion into the MIL53(Fe) positive electrode. In this paper, we combine firstprinciples density functional calculations and local chemical bond analyses to fully interpret the redox mechanism of this material. Its reactivity versus elemental lithium is investigated as a function of (i) the lithium composition from xLi/Fe ) 0-1, (ii) the lithium distribution over the most probable Li sites, and (iii) the OH/F substitution ratio along the redox chains. The results show that the MIL53(Fe) is a weak antiferromagnet at T ) 0 K with iron ions in the high-spin state (Fe3+, S ) 5/2). It reacts with lithium through a two-step insertion/conversion mechanism. The insertion reaction is perfectly reversible and proceeds in two steps: first, a single-phase reaction whose capacity increases linearly with the fluorine content in the starting material, then a two-phase reaction that ends around xLi/Fe ) 0.5 due to the stabilization of a localized Fe2+/Fe3+ mixed-valence state along the inorganic chains. Further lithium insertion into Li0.5MIL53(Fe) is shown to provoke an irreversible conversion reaction due to a complete loss of the local interactions between the inorganic and organic networks of the MOF architecture. On the basis of this interpretation, several alternatives to improve the capacity of these materials can be proposed by means of appropriate ligand functionalization and/or use of electrochemically active molecules within the large open space occurring in such porous materials.

Published
2010
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