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62 results on '"Matthieu, Courty"'

1. Structural and Vibrational Investigations of Mixtures of Cocoa Butter (CB), Cocoa Butter Equivalent (CBE) and Anhydrous Milk Fat (AMF) to Understand Fat Bloom Process

Author

Mustapha El Hadri, Serge Bresson, Albane Lecuelle, Fatiha Bougrioua, Vincent Baeten, Van Hung Nguyen, Vincent Faivre, and Matthieu Courty

Subjects
cocoa butter (CB), cocoa butter equivalent (CBE), milk fatty acid (AMF), MIR and Raman spectroscopy, X-ray diffraction, Technology, Engineering (General). Civil engineering (General), TA1-2040, Biology (General), QH301-705.5, Physics, QC1-999, Chemistry, QD1-999
Abstract

Some studies found that the proportions of cocoa butter (CB), cocoa butter equivalent (CBE) and milk fatty acid (AMF) tend to influence the blooming delay when mixing them. The goal of our research is to determine the effects of the proportion of CB, CBE and AMF on the structural organization of the final mixtures. X-ray, DSC, MIR and Raman spectroscopy were used to analyze the structural features and the vibrational modes of four mixtures: CB + 0.5AMF, CB + AMF, CB + 0.5AMF + CBE and CB + AMF + CBE. At room temperature, the triglycerides are ingredients of CB, and CBE and AMF do not fully exhibit the known crystalline forms V or VI, unlike a recent CB sample. Part of these triglycerides is in the form IV instead. The presence of the latter seems to be a key parameter that favors the deceleration of the transformation to the form VI, which is responsible for the development of fat bloom.

Published
2022
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2. Experimental and Theoretical Investigations of Low-Dimensional BiFeO3 System for Photocatalytic Applications

Author

Manal Benyoussef, Sébastien Saitzek, Nitul S. Rajput, Matthieu Courty, Mimoun El Marssi, and Mustapha Jouiad

Subjects
photocatalysis, BiFeO3 nanoparticles, high energy ball milling, spray pyrolysis, photoelectrochemical measurements, density functional theory, Chemical technology, TP1-1185, Chemistry, QD1-999
Abstract

We report on the fabrication of sub-20 nm BiFeO3 (BFO) nanoparticles using a solid-state approach and preferential leching process. The nanoparticles were subsequently used to deposit, through spray pyrolysis, BFO thin films in a rhombohedral (R3c) crystallographic structure. Then, systematic investigations of the optical and the photocatalytic properties were conducted to determine the effects of the particles size, the microstructure and the increased surface area on their catalytic performances. Especially, improved optical properties were observed, with an optical bandgap energy of 2.20 eV compared to reported 2.7 eV for the bulk system. In addition, high optical absorption was obtained in the UV–visible light region reaching up to 90% at 400 nm. The photoelectrochemical measurements revealed a high photocurrent density under visible light irradiation. Besides, density functional theory calculations were performed on both bulk and thin film BFO structures, revealing an interesting comparison of the electronic, magnetic, ferroelectric and optical properties for bulk and thin film BFO systems. Both theoretical and experimental findings show that the alignment of the band edges of BFO thin film is coherent with good photocatalytic water splitting potential, making them desirable photoanode materials.

Published
2022
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4. Structural details in Li3PS4: Variety in thiophosphate building blocks and correlation to ion transport

Author

Marc-David Braida, Sorina Cretu, Benjamin Porcheron, Ömer Ulaş Kudu, Arnaud Demortière, Virginie Viallet, Benoit Fleutot, Theodosios Famprikis, Matthieu Courty, Thierry Le Mercier, Christian Masquelier, Elodie Salager, 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), Solvay (France), Delft University of Technology (TU Delft), 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), Réseau sur le stockage électrochimique de l'énergie (RS2E), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Université de Montpellier (UM)

Subjects
Conductivity, Materials science, Renewable Energy, Sustainability and the Environment, ϒ-Li3PS4, Energy Engineering and Power Technology, [CHIM.MATE]Chemical Sciences/Material chemistry, Ball-milling, β-Li3PS4, law.invention, Annealing (glass), Amorphous solid, symbols.namesake, 31P MAS NMR, Chemical physics, law, Phase (matter), Magic angle spinning, symbols, Ionic conductivity, General Materials Science, Crystallization, Raman spectroscopy, Raman
Abstract

International audience; Li3PS4 is an attractive solid-electrolyte material that possesses high RT ionic conductivity (10(-4) S.cm(-1) ) but the effects of specific synthesis parameters on the material's local structure and transport properties still demand clarifications. Herein, we highlight the substantial effects of cooling breaks in the mechanochemical synthesis procedure on the formation of a variety of PxSya- moieties and on the transport properties of Li3PS4, through Raman and impedance spectroscopy measurements. We show that ball-milled Li3PS4 (with no subsequent annealing), which is often regarded as ``amorphous/glass/glassy Li3PS4 ``, is not fully amorphous using X-ray diffraction and transmission electron microscopy. Upon subsequent annealing for 1 h above 190 degrees C, beta-Li3PS4 is crystallized and our P-31 magic angle spinning nuclear magnetic resonance spectra suggest that 3 distinct PS43- moieties form, which we refer to as amorphous-, beta-and gamma-type units. Herein, we present a hypothesis to explain the correlation between the ionic conductivity and the distinct PS43- units as a function of the annealing temperature. Our results consolidate the recent reports noting that crystallization of beta-Li3PS4 is not necessary to obtain a high conductivity in ball-milled Li3PS4. Finally, we introduce a phase mixture between beta-Li3PS4 and gamma-Li3PS4 synthesized at 200 degrees C, which is the lowest synthesis temperature yet for gamma-Li3PS4.

Published
2022

6. The formulation of a CMC binder/silicon composite anode for Li-ion batteries: from molecular effects of ball milling on polymer chains to consequences on electrochemical performances

Author

Mariama Ndour, Jean-Pierre Bonnet, Sébastien Cavalaglio, Tristan Lombard, Matthieu Courty, Luc Aymard, Cédric Przybylski, Véronique Bonnet, Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), 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 des technologies de la microélectronique (LTM ), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA), Commissariat à l'énergie atomique et aux énergies alternatives - Laboratoire d'Electronique et de Technologie de l'Information (CEA-LETI), Direction de Recherche Technologique (CEA) (DRT (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA), Institut Parisien de Chimie Moléculaire (IPCM), Chimie Moléculaire de Paris Centre (FR 2769), École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Ecole Superieure de Physique et de Chimie Industrielles de la Ville de Paris (ESPCI Paris), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-École normale supérieure - Paris (ENS-PSL), Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Nantes Université (Nantes Univ)-Université de Montpellier (UM)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), and Université de Montpellier (UM)

Subjects
Chemistry (miscellaneous), [CHIM]Chemical Sciences, General Materials Science
Abstract

The semi-synthetic polysaccharide carboxymethylcellulose (CMC) is one of the most studied and effective polymer binders for silicon-based anodes in Li-ion batteries.

Published
2022

7. Theoretical and experimental studies of chitin nanocrystals treated with ionic liquid or deep eutectic solvent to afford nanochitosan sheets

Author

Catalina Ferreira Funes, Benjamin Bouvier, Christine Cézard, Claudia Fuentealba, Arash Jamali, Matthieu Courty, Caroline Hadad, and Albert Nguyen Van Nhien

Subjects
Materials Chemistry, Physical and Theoretical Chemistry, Condensed Matter Physics, Spectroscopy, Atomic and Molecular Physics, and Optics, Electronic, Optical and Magnetic Materials
Published
2023

8. Structural Polymorphism in Na4Zn(PO4)2 Driven by Rotational Order–Disorder Transitions and the Impact of Heterovalent Substitutions on Na-Ion Conductivity

Author

Vladimir Pomjakushin, François Fauth, Yaroslava Shakhova, Maria A. Kirsanova, Matthieu Courty, Artem M. Abakumov, Jean-Marie Tarascon, Sujoy Saha, Gwenaëlle Rousse, 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), Sorbonne Université (SU), 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), 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 Synchrotron Radiation Facility (ESRF), Paul Scherrer Institute (PSI), Center for Electrochemical Energy Storage, Skolkovo Institute of Science and Technology, 3 Nobel Street, 143026 Moscow, Russia., Institut Universitaire de France (IUF), Ministère de l'Education nationale, de l’Enseignement supérieur et de la Recherche (M.E.N.E.S.R.), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
010405 organic chemistry, Chemistry, Cationic polymerization, [CHIM.MATE]Chemical Sciences/Material chemistry, Electron, Conductivity, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Inorganic Chemistry, Crystallography, Polymorphism (materials science), Vacancy defect, Fast ion conductor, Ionic conductivity, Physical and Theoretical Chemistry, Powder diffraction
Abstract

International audience; Solid electrolytes have regained tremendous interest recently in light of the exposed vulnerability of current rechargeable battery technologies. While designing solid electrolytes, most efforts concentrated on creating structural disorder (vacancies, interstitials, etc.) in a cationic Li/Na sublattice to increase ionic conductivity. In phosphates, the ionic conductivity can also be increased by rotational disorder in the anionic sublattice, via a paddle-wheel mechanism. Herein, we report on Na4Zn(PO4)(2) which is designed from Na3PO4, replacing Na+ with Zn2+ and introducing a vacancy for charge balance. We show that Na4Zn(PO4)(2) undergoes a series of structural transitions under temperature, which are associated with an increase in ionic conductivity by several orders of magnitude. Our detailed crystallographic study, combining electron, neutron, and X-ray powder diffraction, reveals that the room-temperature form, alpha-Na4Zn(PO4)(2), contains orientationally ordered PO4 groups, which undergo partial and full rotational disorder in the high-temperature beta- and gamma-polymorphs, respectively. We furthermore showed that the highly conducting gamma-polymorph could be stabilized at room temperature by ball-milling, whereas the beta-polymorph can be stabilized by partial substitution of Zn2+ with Ga2+ and Al3+. These findings emphasize the role of rotational disorder as an extra parameter to design new solid electrolytes.

Published
2020

9. Two-Dimensional Substitution Series $Na_3P_{1-x}Sb_xS_{4-y}Se_y$: Beyond Static Description of Structural Bottlenecks for $Na^{+}$ Transport

Author

Paul Till, Matthias T. Agne, Marvin A. Kraft, Matthieu Courty, Theodosios Famprikis, Michael Ghidiu, Thorben Krauskopf, Christian Masquelier, Wolfgang G. Zeier, 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), Delft University of Technology (TU Delft), Drexel University, 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), Physikalisch-Chemisches Institut, and Justus-Liebig-Universität Gießen = Justus Liebig University (JLU)

Subjects
General Chemical Engineering, ddc:540, Materials Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, General Chemistry
Abstract

International audience; Highly conductive solid electrolytes are fundamental for all solid-state batteries with low inner cell resistance. Such fast solid electrolytes are often found by systematic substitution experiments in which one atom is exchanged for another, and corresponding changes in ionic transport are monitored. With this strategy, compositions with the most promising transport properties can be identified fast and reliably. However, the substitution of one element does not only influence the crystal structure and diffusion channel size (static) but also the underlying bonding interactions and with it the vibrational properties of the lattice (dynamic). Since both static and dynamic properties influence the diffusion process, simple one-dimensional substitution series only provide limited insights to the importance of changes in the structure and lattice dynamics for the transport properties. To overcome these limitations, we make use of a two-dimensional substitution approach, investigating and comparing the four single-substitution series Na3P1-xSbxS4, Na3P1-xSbxSe4, Na3PS4-ySey, and Na3SbS4-ySey. Specifically, we find that the diffusion channel size represented by the distance between S/Se ions cannot explain the observed changes of activation barriers throughout the whole substitution system. Melting temperatures and the herein newly defined anharmonic bulk modulus-as descriptors for bonding interactions and corresponding lattice dynamics-correlate well with the activation barriers, highlighting the relevance of lattice softness for the ion transport in this class of fast ion conductors.

Published
2022

11. IL versus DES: Impact on chitin pretreatment to afford high quality and highly functionalizable chitosan

Author

Gaël Huet, Arash Jamali, Caroline Hadad, Jose M. González-Domínguez, Dominique Cailleu, Albert Nguyen Van Nhien, Matthieu Courty, Ministère de l’Education Nationale, de la Formation Professionnelle, de l'Enseignement Supérieur et de la Recherche Scientifique (Maroc), Ministerio de Economía, Industria y Competitividad (España), European Commission, González Domínguez, José Miguel, Courty, Matthieu, Cailleu, D., Nguyen van Nhien, A., González Domínguez, José Miguel [0000-0002-0701-7695], Courty, Matthieu [0000-0003-4017-7727], Cailleu, D. [0000-0002-6894-8522], Nguyen van Nhien, A. [0000-0002-1956-1153], Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Reims Champagne-Ardenne (URCA), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), 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), Plateforme Analytique (PFA), and Université de Picardie Jules Verne (UPJV)

Subjects
Deep eutectic solvent, Hermetia illucens, Polymers and Plastics, Chitin, 02 engineering and technology, 010402 general chemistry, 01 natural sciences, Chitosan, chemistry.chemical_compound, Materials Chemistry, Food science, Functionalization, biology, Organic Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, biology.organism_classification, Fatty acid, 0104 chemical sciences, Shrimp, Oleic acid, chemistry, Acetylation, Room temperature ionic liquid, 0210 nano-technology
Abstract

7 figures, 2 tables.-- Supporting information available.-- © 2021. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/, Chitin is mainly extracted from crustaceans, but this resource is seasonally dependent and can represent a major drawback to satisfy the traceability criterion for high valuable applications. Insect resources are valuable alternatives due to their lower mineral content. However, the deacetylation of chitin into chitosan is still an expensive process. Therefore, we herein compare the impact of both DES/IL-pretreatments on the efficiency of the chemical deacetylation of chitin carried out over two insect sources (Bombyx eri, BE and Hermetia illucens, HI) and shrimp shells (S). The results showed that chitosans obtained from IL-pretreated chitins from BE larva, present lower acetylation degrees (13–17%) than DES-pretreated samples (18–27%). A selective N-acylation reaction with oleic acid has also been performed on the purest and most deacetylated chitosans leading to high substitution degrees (up to 27%). The overall approach validates the proper chitin source and processing methodology to achieve high quality and highly functionalizable chitosan., ANVN thanks the ministère de l'éducation nationale, de l'enseignement supérieur et de la recherche for financial support. J.M.G.-D. greatly acknowledges the Spanish MINEICO for his ‘Juan de la Cierva Incorporation' contract, and associated research funds (ref. IJCI-2016-27789), as well as financial support from the regional government of Aragón (Grupo Reconocido DGA T03_17R, FEDER/UE and DGA-T03_20R).

Published
2021

12. A New Superionic Plastic Polymorph of the Na+ Conductor Na3PS4

Author

Benoit Fleutot, Jean-Noël Chotard, Theodosios Famprikis, M. Saiful Islam, Christian Masquelier, James A. Dawson, François Fauth, Emmanuelle Suard, Oliver Clemens, Matthieu Courty, Delft University of Technology (TU Delft), CELLS ALBA, Barcelona 08290, Spain, University of Stuttgart, Institut Laue-Langevin (ILL), 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), 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), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and University of Bath [Bath]

Subjects
Materials science, Leverage (negotiation), Condensed matter physics, General Chemical Engineering, Biomedical Engineering, Ionic conductivity, General Materials Science, [CHIM.MATE]Chemical Sciences/Material chemistry, Electrical conductor, Conductor
Abstract

International audience; Na3PS4 is one of the most promising Na+ conductors, relevant for applications that can leverage its high ionic conductivity, such as solid-state batteries. Currently, two crystalline phases of the material have been identified, and it has been thought to melt above 500 degrees C. In contrast, based on diffraction, ab initio simulations, impedance spectroscopy, and thermal analysis, we show that Na3PS4 remains solid above this temperature and transforms to a third polymorph, gamma, exhibiting fast-ion conduction and an orthorhombic crystal structure. We show that the fast Na+-conduction is associated with rotational motion of the thiophosphate polyanions pointing to a plastic crystal. These findings are of major importance for the development and understanding of new polyanion-based solid electrolytes.

Published
2019

13. Insights into the Rich Polymorphism of the Na

Author

Theodosios, Famprikis, Houssny, Bouyanfif, Pieremanuele, Canepa, Mohamed, Zbiri, James A, Dawson, Emmanuelle, Suard, François, Fauth, Helen Y, Playford, Damien, Dambournet, Olaf J, Borkiewicz, Matthieu, Courty, Oliver, Clemens, Jean-Noël, Chotard, M Saiful, Islam, and Christian, Masquelier

Subjects
Article
Abstract

Solid electrolytes are crucial for next-generation solid-state batteries, and Na3PS4 is one of the most promising Na+ conductors for such applications, despite outstanding questions regarding its structural polymorphs. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 over a wide temperature range 30 < T < 600 °C through combined experimental–computational analysis. Although Bragg diffraction experiments indicate a second-order phase transition from the tetragonal ground state (α, P4̅21c) to the cubic polymorph (β, I4̅3m) above ∼250 °C, pair distribution function analysis in real space and Raman spectroscopy indicate remnants of a tetragonal character in the range 250 < T < 500 °C, which we attribute to dynamic local tetragonal distortions. The first-order phase transition to the mesophasic high-temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid-like dynamics for sodium-cations (translational) and thiophosphate-polyanions (rotational) evident by inelastic neutron and Raman spectroscopies, as well as pair-distribution function and molecular dynamics analyses. These results shed light on the rich polymorphism of Na3PS4 and are relevant for a range host of high-performance materials deriving from the Na3PS4 structural archetype.

Published
2021

14. Insights into the rich polymorphism of the Na+ ion conductor Na3PS4 from the perspective of variable-temperature diffraction and spectroscopy

Author

Damien Dambournet, Helen Y. Playford, Pieremanuele Canepa, Houssny Bouyanfif, Matthieu Courty, Mohamed Zbiri, Emmanuelle Suard, Jean-Noël Chotard, Saiful Islam, Christian Masquelier, François Fauth, Theodosios Famprikis, Olaf J. Borkiewicz, and James A. Dawson

Subjects
Phase transition, Tetragonal crystal system, symbols.namesake, Crystallography, Materials science, symbols, Fast ion conductor, Pair distribution function, Raman spectroscopy, Spectroscopy, Ground state, Inelastic neutron scattering
Abstract

Solid electrolytes are crucial for next generation solid state batteries and Na3PS4 is one of the most promising Na+ conductors for such applications. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 under the effect of temperature in the range 30 < T < 600 °C through combined experimental-computational analysis. Although x ray Bragg diffraction experiments indicate a second order phase transition from the tetragonal ground state (α, P-421c) to the cubic polymorph (β, I-43m), pair distribution function analysis in real space and Raman spectroscopy indicate remnants of tetragonal character in the range 250 < T < 500 °C which we attribute to dynamic local tetragonal distortions. The first order phase transition to the mesophasic high temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid like diffusive dynamics for sodium-cations (translative) and thiophosphate-polyanions (rotational) evident by inelastic neutron- and Raman- spectroscopies, as well as pair-distribution function and molecular dynamics. These results shed light on the rich polymorphism in Na3PS4 and are relevant for a host of high performance materials deriving from the Na3PS4 structural archetype.

Published
2021

15. The Polymorphs of the Na+ Ion Conductor Na3PS4 from the Perspective of Variable Temperature Diffraction and Spectroscopy

Author

Mohamed Zbiri, Saiful Islam, Emmanuelle Suard, Houssny Bouyanfif, Theodosios Famprikis, Helen Y. Playford, Olaf J. Borkiewicz, Christian Masquelier, Matthieu Courty, James A. Dawson, Damien Dambournet, Pieremanuele Canepa, Jean-Noël Chotard, and François Fauth

Subjects
Phase transition, Tetragonal crystal system, symbols.namesake, Materials science, Fast ion conductor, symbols, Analytical chemistry, Pair distribution function, Spectroscopy, Ground state, Raman spectroscopy, Inelastic neutron scattering
Abstract

Solid electrolytes are crucial for next generation solid state batteries and Na3PS4 is one of the most promising Na+ conductors for such applications. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na3PS4 under the effect of temperature in the range 30 < T < 600 °C through combined experimental-computational analysis. Although x ray Bragg diffraction experiments indicate a second order phase transition from the tetragonal ground state (α, P-421c) to the cubic polymorph (β, I-43m), pair distribution function analysis in real space and Raman spectroscopy indicate remnants of tetragonal character in the range 250 < T < 500 °C which we attribute to dynamic local tetragonal distortions. The first order phase transition to the mesophasic high temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid like diffusive dynamics for sodium-cations (translative) and thiophosphate-polyanions (rotational) evident by inelastic neutron- and Raman- spectroscopies, as well as pair-distribution function and molecular dynamics. These results shed light on the rich polymorphism in Na3PS4 and are relevant for a host of high performance materials deriving from the Na3PS4 structural archetype.

Published
2021

16. Insights into the Rich Polymorphism of the Na+ Ion Conductor Na3PS4 from the Perspective of Variable-Temperature Diffraction and Spectroscopy

Author

Emmanuelle Suard, M. Saiful Islam, Houssny Bouyanfif, Olaf J. Borkiewicz, Jean-Noël Chotard, Mohamed Zbiri, Theodosios Famprikis, Matthieu Courty, Christian Masquelier, Oliver Clemens, François Fauth, James A. Dawson, Helen Y. Playford, Pieremanuele Canepa, Damien Dambournet, 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), University of Bath [Bath], 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 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), Laboratoire de Physique de la Matière Condensée - UR UPJV 2081 (LPMC), Université de Picardie Jules Verne (UPJV), National University of Singapore (NUS), Institut Laue-Langevin (ILL), ILL, Newcastle University [Newcastle], ALBA Synchrotron light source [Barcelone], STFC Rutherford Appleton Laboratory (RAL), Science and Technology Facilities Council (STFC), PHysicochimie des Electrolytes et Nanosystèmes InterfaciauX (PHENIX), Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Argonne National Laboratory [Lemont] (ANL), University of Stuttgart, Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Phase transition, Materials science, General Chemical Engineering, 02 engineering and technology, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, symbols.namesake, Tetragonal crystal system, Chemical structure, Materials Chemistry, Fast ion conductor, Spectroscopy, Bragg's law, Pair distribution function, General Chemistry, Lattices, [CHIM.MATE]Chemical Sciences/Material chemistry, Atmospheric temperature range, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Crystallography, Phase transitions, Raman spectroscopy, symbols, Group theory, 0210 nano-technology
Abstract

International audience; Solid electrolytes are crucial for next-generation solid-state batteries, and Na 3 PS 4 is one of the most promising Na + conductors for such applications, despite outstanding questions regarding its structural polymorphs. In this contribution, we present a detailed investigation of the evolution in structure and dynamics of Na 3 PS 4 over a wide temperature range 30 < T < 600°C through combined experimental−computational analysis. Although Bragg diffraction experiments indicate a second-order phase transition from the tetragonal ground state (α, P4̅ 2 1 c) to the cubic polymorph (β, I4̅ 3m) above ∼250°C, pair distribution function analysis in real space and Raman spectroscopy indicate remnants of a tetragonal character in the range 250 < T < 500°C, which we attribute to dynamic local tetragonal distortions. The first-order phase transition to the mesophasic high-temperature polymorph (γ, Fddd) is associated with a sharp volume increase and the onset of liquid-like dynamics for sodium-cations (translational) and thiophosphate-polyanions (rotational) evident by inelastic neutron and Raman spectroscopies, as well as pair-distribution function and molecular dynamics analyses. These results shed light on the rich polymorphism of Na 3 PS 4 and are relevant for a range host of high-performance materials deriving from the Na 3 PS 4 structural archetype.

Published
2021

19. Carbon-Loaded Flexible Electrode Films for Li-O2 Cells: Preparation, Porosity, Homogeneity and Electrochemical Characterization

Author

Matthieu Courty, Christine Surcin, Caroline Gaya, Dominique Larcher, and Alejandro A. Franco

Subjects
chemistry.chemical_classification, Materials science, Chemical engineering, chemistry, Electrode, Homogeneity (physics), chemistry.chemical_element, Texture (crystalline), Polymer, Leaching (metallurgy), Porosity, Electrochemistry, Carbon
Abstract

Porous (up to 70 vol. %) self-standing flexible carbon/polymer (Ketjen Black / PVdF-HFP) film electrodes are produced by leaching out a plasticizer-porogen agent (DBP = DiButyl Phtalate) from precursor films (80% ³ DBP w% ³ 40%). Textural analysis reveals that i) these films exhibit copious initial macroporosity, ii) extra open macro- and then meso-porosity are created along the leaching, iii) this leaching process impacts the internal films texture resulting in a partial closing of the pre-existing porosity, iv) only films with the lowest initial DBP contents (≤ 60 w%) are homogeneous in composition/porosity/texture. In Li/O2 cells, the first discharge capacities of these films are compared to those calculated assuming a total filling of this porosity by electrochemically formed solid Li2O2 (2700 mAh.cm-3 of pores). Up to 80 % of the maximum capacity can be reached (i.e. 80 % of the porosity filled by Li2O2), confirming the positive attributes of mixed interconnected macro/meso porosity. This is further emphasized by the very low capacities obtained with electrodes having similar porosity vol. % but totally different internal texture (GDL). These conclusions can be made despite a large discrepancy in the data, even for homogeneous films, due to reproducibility issues intrinsic to the system.

Published
2020

20. Mechanochemical synthesis and ion transport properties of Na3OX (X = Cl, Br, I and BH4) antiperovskite solid electrolytes

Author

Matthieu Courty, Christian Masquelier, Oliver Clemens, Ulas Kudu, Theodosios Famprikis, Ernest Ahiavi, James A. Dawson, M. Saiful Islam, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Borohydride, Materials science, Ab initio, Energy Engineering and Power Technology, 02 engineering and technology, Electrolyte, Molecular dynamics, 010402 general chemistry, 01 natural sciences, Ion, Antiperovskite, Synthesis, Ionic conductivity, Fast ion conductor, [CHIM]Chemical Sciences, SDG 7 - Affordable and Clean Energy, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, Ion transporter, Renewable Energy, Sustainability and the Environment, 021001 nanoscience & nanotechnology, Ball-milling, 0104 chemical sciences, Dielectric spectroscopy, Physical chemistry, 0210 nano-technology
Abstract

The push towards the development of next-generation solid-state batteries has motivated the search for novel solid electrolyte materials. Sodium antiperovskites represent a structural family of ion conductors that has emerged as a result, with expected advantages in terms of composition tuning, electrochemical stability, mechanical softness and high ionic conductivity. Here, we report the mechanochemical synthesis of several materials in this structural family, including novel mixed-halide compositions such as Na3OCl0.5(BH4)0.5, Na3OBr0.5(BH4)0.5 Na3OI0.5(BH4)0.5 and Na3OCl0.33Br0.33(BH4)0.33. We rationalize the effect of halide substitution on the structure and ion transport properties of these materials through diffraction, impedance spectroscopy and molecular dynamics. We conclude with a discussion on Na3OBH4, which has recently been reported to be a fast ion conductor, owing to the rotational disorder of the complex superhalide anion BH4−. We are unable to reproduce the reported high ionic conductivity of Na3OBH4 neither by experiment nor ab initio simulation.

Published
2020

21. Overview on Lithium-Ion Battery 3D-Printing By Means of Material Extrusion

Author

Carine Davoisne, Benoit Fleutot, Matthieu Courty, Hugues Tortajada, Stéphane Panier, Michel Armand, Kalappa Prashantha, Loic Dupont, Sylvie Grugeon, Alexis Maurel, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Centre National de la Recherche Scientifique (CNRS)-Université de Picardie Jules Verne (UPJV), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), and Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Battery (electricity), chemistry.chemical_classification, Thermoplastic, Fused deposition modeling, Inkwell, Computer science, business.industry, 3D printing, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, Lithium-ion battery, 0104 chemical sciences, law.invention, [SPI]Engineering Sciences [physics], chemistry, law, Deposition (phase transition), Extrusion, 0210 nano-technology, business, Process engineering
Abstract

In parallel with the considerable investigations on renewable energy sources, electrical energy storage systems used to store the energy produced now and to provide it when needed have received much attention lately.1 Amongst them, lithium-ion batteries (LIB) are today the most employed in a huge range of purposes including cellphones, laptops or even electric vehicles. Current LIB consists in a planar arrangement (2D) in which the different parts of the battery (positive and negative electrodes, separator, current collectors) are rolled or stacked. Unfortunately, in this type of 2D configuration, lithium ions diffuse only along one dimension. Additive manufacturing (AM) technologies, also called 3D-printing processes, could enable the production of much more complex 3D architectures thus allowing diffusion of the lithium cations towards two or three-dimensions. Advantage of those 3D designs is that the electrochemical active surface area is expected to increase as well as the battery specific capacity and power.2 On the other hand, AM could also allow the direct incorporation of LIB within the final object, thus enabling the possibility to maximize the energy storage capabilities while reducing the dead volume and weight. Amongst the various AM available technologies, we focused our work on the Fused Deposition Modeling (FDM) process using a thermoplastic filament as material source for the 3D-printer. In this presentation, the formulation of composite PLA-based filaments specially designed to print each parts of the LIB (with liquid electrolyte) will be described.3,4 The active material composition within the negative and positive electrodes (graphite and lithium iron phosphate (LiFePO4) respectively), was increased as high as possible in order to enhance the electrochemical performances. Furthermore, the addition of a plasticizer was required to maintain enough mechanical strength while, in the meantime, carbon black was added to confer adequate electrical properties. The impact of ceramic additives on ionic conductivity in the separator was also investigated. From the optimized filaments compositions, stepwise and then “one-shot” 3D-printing of complete LiFePO4/graphite battery cells of any shapes were carried out (Figure 1). In order to prevent short-circuits, classical 3D-printing parameters such as the infill patterns and infill density were investigated for the LIB separator improvement. Finally, this presentation will introduce our latest results5 regarding the printability of a polyethylene oxide/lithium bis(trifluoromethanesulfonyl)imide (PEO/LiTFSI) filament (2.18 × 10−3 S cm−1 at 90 °C) optimized to be used as solid polymer electrolyte in a lithium-ion battery. This presentation, by combining both battery and 3D-printing understandings, will tackle various electrochemical (thickness, electronic and ionic conductivity, liquid electrolyte uptake) and 3D-printing parameters (infill density, infill pattern, perimeters, over and under-extrusion, retraction), which clearly paves the way for enhanced 3D-printed LIB. References: [1] Tarascon, J. M. & Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 414, 359-367, doi:10.1038/35104644 (2001). [2] Long, J. W., Dunn, B., Rolison, D. R. & White, H. S. Three-dimensional battery architectures. Chemical Reviews 104, 4463-4492, doi:10.1021/cr020740l (2004). [3] Maurel, A. et al. Highly Loaded Graphite-Polylactic Acid Composite-Based Filaments for Lithium-Ion Battery Three-Dimensional Printing. Chemistry of Materials 30, 7484-7493, doi:10.1021/acs.chemmater.8b02062 (2018). [4] Maurel, A. et al. Three-Dimensional Printing of a LiFePO4/Graphite Battery Cell via Fused Deposition Modeling. Scientific Reports 9, 18031, doi:10.1038/s41598-019-54518-y (2019). [5] Maurel, A. et al. Poly(Ethylene Oxide)−LiTFSI Solid Polymer Electrolyte Filaments for Fused Deposition Modeling Three-Dimensional Printing. Journal of The Electrochemical Society 167, 070536, doi:10.1149/1945-7111/ab7c38 (2020). Figure 1

Published
2020

22. High reactivity of the nickel-rich LiNi1-x-yMnxCoyO2 layered materials surface towards H2O/CO2 atmosphere and LiPF6-based electrolyte

Author

Dominique Cailleu, Sylvie Grugeon, Stéphane Laruelle, Pierre Tran-Van, Ana Cristina Martinez, Matthieu Courty, Bruno Delobel, 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), Technocentre Renault [Saint-Quentin-en-Yvelines], RENAULT, 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), Plateforme Analytique (PFA), Université de Picardie Jules Verne (UPJV), Technocentre Renault [Guyancourt], Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Thermogravimetric analysis, Materials science, Inorganic chemistry, Oxide, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, Electrolyte, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Reactivity (chemistry), Electrical and Electronic Engineering, Physical and Theoretical Chemistry, ComputingMilieux_MISCELLANEOUS, Renewable Energy, Sustainability and the Environment, Thermal decomposition, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Nickel, chemistry, 13. Climate action, Inductively coupled plasma atomic emission spectroscopy, Hydroxide, 0210 nano-technology
Abstract

Storage of nickel-rich LiNi1-x-yMnxCoyO2 positive active materials under improper environmental conditions brings about undesirable surface reactions causing poor Li-ion cell electrochemical performances and gas generation. In this paper, a detailed stepwise investigation of the increasing reactivity of 532, 622, 811 and 901 NMC materials towards a specific H2O/CO2 atmosphere is reported. Water-soluble salts as lithium carbonate, hydroxide and sulfates are accurately quantified thanks to acid-base titration and inductively coupled plasma atomic emission spectroscopy techniques. On the other hand, the presence of insoluble species as transition metal oxyhydroxides and oxides is unveiled through a thermal decomposition study using thermogravimetric mass spectrometer coupling technique. Their formation and thermal decomposition mechanisms are proposed after careful analysis of the characteristic mass loss and O2, CO2 and H2O evolution profile in the 50–500 °C region. Interestingly, the results also highlight an in situ lithiated layered oxide material reformation reaction. To assess their chemical reactivity towards LiPF6-based electrolyte, the latter was analyzed through 19F nuclear magnetic resonance after storage with various reference salts and 811 NMC. LiPO2F2 is detected from storage tests with Li2CO3, Li2O and Li2SO4, and fluorophosphate-type molecules are detected from LiOH; this experiment can help discriminate between LiOH and Li2O as NMC surface species.

Published
2020

23. New biobased-zwitterionic ionic liquids: efficiency and biocompatibility for the development of sustainable biorefinery processes

Author

Catherine Sarazin, Monica Araya-Farias, Benjamin Bouvier, Christine Cézard, Eric Husson, Ranim Alayoubi, Gaël Huet, Isabelle Gosselin, Caroline Hadad, Matthieu Courty, Romain Roulard, Albert Nguyen Van Nhien, Sylvain Laclef, Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Institut Galien Paris-Saclay (IGPS), Institut de Chimie du CNRS (INC)-Université Paris-Saclay-Centre National de la Recherche Scientifique (CNRS), Génie Enzymatique et Cellulaire (GEC), Université de Technologie de Compiègne (UTC)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS), Université de Picardie Jules Verne (UPJV), 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 Reims Champagne-Ardenne (URCA), Laboratoire des Glucides (LG), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Picardie Jules Verne (UPJV), Biologie des Plantes et Innovation - UR UPJV 3900 (BIOPI), Université de Picardie Jules Verne (UPJV)-Transfrontalière BioEcoAgro - UMR 1158 (BioEcoAgro), Université d'Artois (UA)-Université de Liège-Université de Picardie Jules Verne (UPJV)-Université du Littoral Côte d'Opale (ULCO)-Université de Lille-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-JUNIA (JUNIA), Université catholique de Lille (UCL)-Université catholique de Lille (UCL)-Université d'Artois (UA)-Université de Liège-Université du Littoral Côte d'Opale (ULCO)-Université de Lille-Institut National de Recherche pour l’Agriculture, l’Alimentation et l’Environnement (INRAE)-JUNIA (JUNIA), and Université catholique de Lille (UCL)-Université catholique de Lille (UCL)

Subjects
Biocompatibility, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Hydrolysis, Environmental Chemistry, Organic chemistry, Ethanol fuel, [SDV.IB.BIO]Life Sciences [q-bio]/Bioengineering/Biomaterials, Alkyl, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, 010405 organic chemistry, [SDE.IE]Environmental Sciences/Environmental Engineering, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [SDV.BBM.BM]Life Sciences [q-bio]/Biochemistry, Molecular Biology/Molecular biology, Biorefinery, Pollution, [SDV.MP.BAC]Life Sciences [q-bio]/Microbiology and Parasitology/Bacteriology, 6. Clean water, Yeast, 0104 chemical sciences, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, visual_art, Ionic liquid, visual_art.visual_art_medium, Sawdust
Abstract

International audience; A new family of biobased-zwitterionic ionic liquids (ZILs) have been synthesized starting from the renewable resource L-histidine natural amino acid and varying the lengths of the alkyl chains. These ZIL derivatives were firstly studied for their biocompatibility with different microorganisms including bacteria, molds and yeast. The obtained MIC values indicated that all the microorganisms were 5 to 25 times more tolerant to ZIL derivatives than the robust 1-ethyl-3-methylimidazolium acetate [C2mim][OAc] used as a reference. Modeling studies also revealed that the presence of the cation and the anion on the same skeleton together with the length of the N-alkyl chain would govern the biocompatibility of these neoteric solvents. Among the different synthesized ZILs, the N,N′-diethyl derivative has been demonstrated to be a suitable eco-alternative to the classically used [C2mim][OAc] for efficient pretreatment of harwood sawdust leading to a significant improvement of enzymatic saccharification. In addition, with up to a 5% w/v concentration in the culture medium, ZILs did not induce deleterious effects on fermentative yeast growth nor ethanol production.

Published
2020

24. Structural Polymorphism in Na

Author

Sujoy, Saha, Gwenaëlle, Rousse, Matthieu, Courty, Yaroslava, Shakhova, Maria, Kirsanova, François, Fauth, Vladimir, Pomjakushin, Artem M, Abakumov, and J M, Tarascon

Abstract

Solid electrolytes have regained tremendous interest recently in light of the exposed vulnerability of current rechargeable battery technologies. While designing solid electrolytes, most efforts concentrated on creating structural disorder (vacancies, interstitials, etc.) in a cationic Li/Na sublattice to increase ionic conductivity. In phosphates, the ionic conductivity can also be increased by rotational disorder in the anionic sublattice, via a paddle-wheel mechanism. Herein, we report on Na

Published
2020

25. Straightforward extraction and selective bioconversion of high purity chitin from Bombyx eri larva: Toward an integrated insect biorefinery

Author

Virginie Lambertyn, Catherine Sarazin, Arash Jamali, Sylvain Laclef, Albert Nguyen Van Nhien, Monica Araya Farias, Caroline Hadad, Gaël Huet, Matthieu Courty, Isabelle Gosselin, Ranim Alayoubi, Eric Husson, Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Génie Enzymatique et Cellulaire (GEC), Université de Technologie de Compiègne (UTC)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS), Université de Picardie Jules Verne (UPJV), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), and Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
[SDV.BIO]Life Sciences [q-bio]/Biotechnology, Polymers and Plastics, Bioconversion, Microorganism, Chitin, 02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Hydrolysate, chemistry.chemical_compound, Crustacea, Materials Chemistry, Animals, Bombyx, Chromatography, biology, Chemistry, Organic Chemistry, Extraction (chemistry), 021001 nanoscience & nanotechnology, biology.organism_classification, Biorefinery, 0104 chemical sciences, Shrimp, Larva, 0210 nano-technology
Abstract

International audience; Keywords: Chitin Insect biorefinery Room temperature ionic liquid Enzymatic digestibility Fermentescibility A B S T R A C T Chitins of different purity grades (45%, 89.7% and 93.3%) were efficiently extracted from Bombyx eri larva and fully physico-chemically characterized. Compared to commercially available and extracted α-chitin from shrimp shell, the collected data showed that insect chitins had similar characteristics in terms of crystallographic structures (α-chitin), thermal stability and degree of acetylation (> 87%). The major differences lay in the crystallinity indexes (66% vs 75% for shrimp chitin) and in the morphological structures. Furthermore, low ash contents were determined for the insect chitins (1.90% vs 21.73% for shrimp chitin), making this chitin extraction and purification easier, which is highly valuable for an industrial application. Indeed, after only one step (deproteinization), the obtained chitin from Bombyx eri showed higher purity grade than the one extracted from shrimp shells under the same conditions. Insect chitins were then subjected to room temperature ionic liquid (RTIL) pretreatment prior to enzymatic degradation and presented a higher enzymatic digestibility compared to commercial one whatever their purity grade and would be thus a more relevant source for the selective production of N-acetyl-D-glucosamine (899.2 mg/g of chitin-2 steps vs 760 mg/g of chitin com). Moreover, for the first time, the fermentescibility of chitin hydrolysates was demonstrated with Scheffersomyces stipitis used as ethanologenic microorganism.

Published
2020

27. Highly Loaded Graphite–Polylactic Acid Composite-Based Filaments for Lithium-Ion Battery Three-Dimensional Printing

Author

Hugues Tortajada, Stéphane Panier, Kalappa Prashantha, Benoit Fleutot, Sylvie Grugeon, Matthieu Courty, Michel Armand, Loic Dupont, Alexis Maurel, Ecole nationale supérieure Mines-Télécom Lille Douai (IMT Lille Douai), and Institut Mines-Télécom [Paris] (IMT)

Subjects
Materials science, General Chemical Engineering, Diffusion, Composite number, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, Lithium-ion battery, 0104 chemical sciences, [SPI]Engineering Sciences [physics], chemistry.chemical_compound, Polylactic acid, chemistry, Dimension (vector space), Three dimensional printing, Electrode, Materials Chemistry, Graphite, Composite material, 0210 nano-technology
Abstract

Actual parallel-plate architecture of lithium-ion batteries consists of lithium-ion diffusion in one dimension between the electrodes. To achieve higher performances in terms of specific capacity and power, configurations enabling lithium-ion diffusion in two or three dimensions is considered. With a view to build these complex three-dimensional (3D) battery architectures avoiding the electrodes interpenetration issues, this work is focused on fused deposition modeling (FDM). In this study, the formulation and characterization of a 3D-printable graphite/polylactic acid (PLA) filament, specially designed to be used as negative electrode in a lithium-ion battery and to feed a conventional commercially available FDM 3D printer, is reported. The graphite active material loading in the produced filament is increased as high as possible to enhance the electrochemical performance, while the addition of various amounts of plasticizers such as propylene carbonate, poly(ethylene glycol) dimethyl ether average Mn ∼ 2000, poly(ethylene glycol) dimethyl ether average Mn ∼ 500, and acetyl tributyl citrate is investigated to provide the necessary flexibility to the filament to be printed. Considering the optimized plasticizer composition, an in-depth study is carried out to identify the electrical and electrochemical impact of carbon black and carbon nanofibers as conductive additives. © 2018 American Chemical Society.

Published
2018

28. Oxidative decomposition products of synthetic NaFePO4 marićite: nano-textural and electrochemical characterization

Author

Sorina Cretu, Matthieu Courty, Rénald David, Arnaud Demortière, Fabrice Brunet, Camille Crouzet, Nadir Recham, Institut des Sciences de la Terre (ISTerre), and Institut Français des Sciences et Technologies des Transports, de l'Aménagement et des Réseaux (IFSTTAR)-Institut national des sciences de l'Univers (INSU - CNRS)-Institut de recherche pour le développement [IRD] : UR219-Université Savoie Mont Blanc (USMB [Université de Savoie] [Université de Chambéry])-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes [2016-2019] (UGA [2016-2019])

Subjects
Monosodium phosphate, Chemistry, 05 social sciences, [SDU.STU]Sciences of the Universe [physics]/Earth Sciences, Maricite, Thermal treatment, Electrochemistry, Decomposition, chemistry.chemical_compound, Geochemistry and Petrology, Iron oxalate, 0502 economics and business, [SDE]Environmental Sciences, Fast ion conductor, 050211 marketing, Iron phosphate, 050203 business & management, Nuclear chemistry
Abstract

International audience; 44 Single-phase marićite, NaFePO4, was synthesized from monosodium phosphate and 45 iron oxalate at 750°C, at atmospheric pressure. Thermal treatment of synthetic marićite in air 46 indicated oxidative decomposition into Na3Fe 3+ 2(PO4)3 nasicon and-Fe2O3 at temperatures 47 above 225°C. Intergrowth of the reaction products is found to occur at the nanoscale without 48 identified crystallographic relationship with the marićite precursor. Electrochemical activity of 49 the reaction product is confirmed with the reversible insertion of one Na at 2.55 V vs Na + /Na 0. 50 Keywords: sodium iron phosphate; marićite; sodium-ion batteries; oxidative decomposition; 51 NASICON 52 53 54

Published
2019

29. Three-Dimensional Printing of a LiFePO4/Graphite Battery Cell via Fused Deposition Modeling

Author

Hugues Tortajada, Alexis Maurel, Michel Armand, Kalappa Prashantha, Matthieu Courty, Sylvie Grugeon, Stéphane Panier, Benoit Fleutot, Loic Dupont, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), and Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Materials science, lcsh:Medicine, 02 engineering and technology, Electrolyte, 010402 general chemistry, Electrochemistry, 01 natural sciences, Article, law.invention, chemistry.chemical_compound, Batteries, law, [CHIM]Chemical Sciences, Graphite, Ceramic, lcsh:Science, Separator (electricity), Multidisciplinary, Fused deposition modeling, Lithium iron phosphate, lcsh:R, 021001 nanoscience & nanotechnology, Mechanical engineering, 0104 chemical sciences, Chemical engineering, chemistry, visual_art, Electrode, visual_art.visual_art_medium, lcsh:Q, 0210 nano-technology
Abstract

Among the 3D-printing technologies, fused deposition modeling (FDM) represents a promising route to enable direct incorporation of the battery within the final 3D object. Here, the preparation and characterization of lithium iron phosphate/polylactic acid (LFP/PLA) and SiO2/PLA 3D-printable filaments, specifically conceived respectively as positive electrode and separator in a lithium-ion battery is reported. By means of plasticizer addition, the active material loading within the positive electrode is raised as high as possible (up to 52 wt.%) while still providing enough flexibility to the filament to be printed. A thorough analysis is performed to determine the thermal, electrical and electrochemical effect of carbon black as conductive additive in the positive electrode and the electrolyte uptake impact of ceramic additives in the separator. Considering both optimized filaments composition and using our previously reported graphite/PLA filament for the negative electrode, assembled and “printed in one-shot” complete LFP/Graphite battery cells are 3D-printed and characterized. Taking advantage of the new design capabilities conferred by 3D-printing, separator patterns and infill density are discussed with a view to enhance the liquid electrolyte impregnation and avoid short-circuits.

Published
2019

30. Polymorphism in Li4Zn(PO4)2 and Stabilization of its Structural Disorder to Improve Ionic Conductivity

Author

Jean-Marie Tarascon, Gwenaëlle Rousse, Sujoy Saha, Daniel Alves Dalla Corte, Matthieu Courty, Ignacio Blazquez Alcover, Université Pierre et Marie Curie - Paris 6 (UPMC), 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), 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), 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), and Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Materials science, Crystal chemistry, General Chemical Engineering, 02 engineering and technology, General Chemistry, Crystal structure, Conductivity, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 0104 chemical sciences, Crystallography, Polymorphism (materials science), Materials Chemistry, Fast ion conductor, [CHIM]Chemical Sciences, Ionic conductivity, Orthorhombic crystal system, 0210 nano-technology, Monoclinic crystal system
Abstract

International audience; Realization of the vulnerability of current rechargeable battery systems drives the research of solid electrolytes. In the search for a new Li ion conductor, we explore the rich crystal chemistry of Li 4 Zn(PO 4) 2 which presents a low temperature monoclinic (α-) and a high temperature orthorhombic (β-) polymorph. We solved the crystal structure of the β-phase and found that it has a disordered Li/Zn-sublattice while showing the largest conductivity; however it could not be stabilized at room temperature by quenching. We discovered that the partial substitution of Zn 2+ with Ga 3+ in Li 4-x Zn 1-x Ga x (PO 4) 2 first leads to an intermediate β' phase. Increasing the Ga content to 0.5 mol pfu. enables to stabilize the pure β-phase at room temperature, which exhibits a conductivity by several orders of magnitudes higher than the pristine sample. The crystal structures of the new β'/β-phases have been solved to elucidate the conduction mechanism, which confirms the high sensitivity of ionic conductivity on disorder.

Published
2018

31. Coupled X-ray diffraction and electrochemical studies of the mixed Ti/V-containing NASICON: Na2TiV(PO4)3

Author

Fabien Lalère, Matthieu Courty, Vincent Seznec, Christian Masquelier, Jean-Noël Chotard, 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), 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 ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Diffraction, Materials science, Renewable Energy, Sustainability and the Environment, Solid-state, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Redox, 0104 chemical sciences, Crystallography, X-ray crystallography, Fast ion conductor, General Materials Science, 0210 nano-technology, Intermediate composition
Abstract

International audience; The solid state synthesis of NaTiV(PO4)(3) and Na3TiV(PO4)(3) is reported. Soft chemical oxidation of the latter composition led to NASICON Na2TiV(PO4)(3) with intermediate unit cell parameters (s.g.: R (3) over barc, a = 8.610(3) angstrom, c = 21.755(6) angstrom) when compared to NaTiV(PO4)(3) and Na3TiV(PO4)(3). Coupled structural/electrochemical studies were carried out on Na2TiV(PO4)(3) for oxidation and reduction by operando X-ray diffraction. While the oxidation mechanism towards NaTiV(PO4)(3) is quite simple, the reduction mechanisms involve several mono-and bi-phasic mechanisms leading to Na3TiV(PO4)(3) as an intermediate composition and to Na4TiV(PO4)(3) eventually.

Published
2018

32. Sol-gel synthesis and electrochemical properties extracted by phase inflection detection method of NASICON-type solid electrolytes LiZr 2 (PO 4 ) 3 and Li 1.2 Zr 1.9 Ca 0.1 (PO 4 ) 3

Author

Matthieu Courty, Alice Cassel, Benoit Fleutot, Virginie Viallet, Mathieu Morcrette, 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), Service de physique de l'état condensé (SPEC - UMR3680), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Paris-Saclay-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), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), and Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Battery (electricity), Materials science, Analytical chemistry, chemistry.chemical_element, Context (language use), [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, Electrochemistry, 01 natural sciences, 0104 chemical sciences, Dielectric spectroscopy, chemistry, Phase (matter), Fast ion conductor, Ionic conductivity, General Materials Science, Lithium, 0210 nano-technology
Abstract

International audience; The use of good ionic conductors is a key point in various battery technologies such as Li-air Lithium-Sulfur (Li-S) and All-Solid-State batteries. The determination of the conduction properties as well as the structure in function of temperature and their electrochemical stability are paramount. At the same time, the manufacturing process of these solid electrolytes must be simplified in order to foster the emergence of these technologies. In this context, NASICON-type solid electrolytes LiZr2(PO4)(3) (LZP) and Li1.2Zr1.9Ca0.1(PO4)(3) (LCZP) were synthetized by a new sol-gel method to simplify the synthesis process compared to the solid-state reaction and to reduce the synthesis temperature from 1200 degrees C to 1100 degrees C. The influence of Ca-doping on crystal structure and transport properties was studied in function of temperature and for the first time the electrochemical stability determined. A method, the Phase Inflection Detection (PID), was developed to better determine the transport properties extracted from Electrochemical Impedance Spectroscopy. The ionic conductivity of LCZP is greater than that of LZP by about 2 decades at room temperature due to the stabilization of the high temperature phase at room temperature by Ca-doping, an increase in the number of lithium mobile ions and a better compactness compared with LZP. The impact of sintering temperature and grain boundaries on transport properties is clearly demonstrated and must be taken into account in the future studies of solid electrolytes. The LCZP material is not stable below 0.6 V vs. Li+/Li. It thus presents one of the best electrochemical stabilities, making it a potential candidate for various battery technologies.

Published
2017

33. Nitroxide-Grafted Nanometric Metal Oxides for the Catalytic Oxidation of Sugar

Author

Anne Wadouachi, Mehdi Omri, Matthieu Courty, Gwladys Pourceau, Matthieu Becuwe, Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), and Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Nitroxide mediated radical polymerization, Thermogravimetric analysis, 010405 organic chemistry, Chemistry, Oxide, Infrared spectroscopy, 010402 general chemistry, 01 natural sciences, 0104 chemical sciences, Catalysis, Metal, chemistry.chemical_compound, Chemical engineering, visual_art, Monolayer, visual_art.visual_art_medium, [CHIM]Chemical Sciences, General Materials Science, Hybrid material
Abstract

International audience; A new series of ([2,2,6,6-tetramethylpiperidin-1-yl]oxy) (TEMPO) catalysts supported on nanometric metal oxides (TiO2, AlO2, CeO2) and their efficiency for sugar oxidation are herein described. The preparation of such hybrid catalysts was carried out by modification of a metal oxide surface with a monolayer of phosphonic linker bearing a TEMPO radical. All prepared catalysts were carefully characterized by diffuse reflectance Fourier-transform infrared spectroscopy, thermogravimetric analysis, X-ray diffraction, and transmission electron microscopy. The efficiency of these new hybrid TEMPO supported materials for sugar oxidation was evaluated on methyl α-d-glucoside, as a model carbohydrate. The three hybrid catalysts showed high selectivity, activity, and stability, suggesting a promising potential for rapidly obtaining acid sugar derivatives.

Published
2019

34. Mesoscale Texturation of Organic-Based Negative Electrode Material through in Situ Proton Reduction of Conjugated Carboxylic Acid

Author

Frédéric Sauvage, Matthieu Becuwe, Matthieu Courty, Lionel Fédèle, Sébastien Gottis, Carine Davoisne, Jean-Marie Tarascon, Florent Lepoivre, 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), 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), 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), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-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), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, Université Toulouse III - Paul Sabatier (UT3), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université de Toulouse (UT)

Subjects
chemistry.chemical_classification, In situ, Battery (electricity), Electrode material, Proton, General Chemical Engineering, Carboxylic acid, Inorganic chemistry, 02 engineering and technology, General Chemistry, Conjugated system, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 7. Clean energy, 01 natural sciences, 0104 chemical sciences, chemistry, Materials Chemistry, [CHIM]Chemical Sciences, Reactivity (chemistry), 0210 nano-technology, ComputingMilieux_MISCELLANEOUS
Abstract

In situ proton reduction of the conjugated carboxylic acid during the early stage of the first battery discharge made of NDC/Li half-cell affords enhancing the electrochemical reactivity versus lit...

Published
2019

35. A New Phase of the Na+ Ion Conductor Na3PS4

Author

François Fauth, James A. Dawson, Saiful Islam, Benoit Fleutot, Matthieu Courty, Jean-Noël Chotard, Christian Masquelier, Theodosios Famprikis, and Emmanuelle Suard

Subjects
Diffraction, Materials science, Scattering, Chemical physics, Phase (matter), Neutron diffraction, Fast ion conductor, Density functional theory, Orthorhombic crystal system, Thermal analysis
Abstract

Solid electrolytes are crucial for next‑generation solid‑state batteries and Na3PS4 is one of the most promising Na+ conductors for such applications. At present, two phases of Na3PS4 have been identified and it had been thought to melt above 500 °C. In contrast, we show that it remains solid above this temperature and transforms into a third polymorph, γ, exhibiting superionic behavior. We propose an orthorhombic crystal structure for γ‑Na3PS4 based on scattering density analysis of diffraction data and density functional theory calculations. We show that the Na+ superionic behavior is associated with rotational motion of the thiophosphate polyanions pointing to a rotor phase, based on ab initio molecular dynamics simulations and supported by high‑temperature synchrotron and neutron diffraction, thermal analysis and impedance spectroscopy. These findings are of importance for the development of new polyanion‑based solid electrolytes.

Published
2019

36. Chemical, textural and structural evolution of Ni 1−x O nanoparticles upon isothermal air heating

Author

Kevin Croué, Matthieu Courty, Dominique Larcher, 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), 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 ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Materials science, Nanoparticle, chemistry.chemical_element, [CHIM.MATE]Chemical Sciences/Material chemistry, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 01 natural sciences, Oxygen, Isothermal process, 0104 chemical sciences, Crystallography, chemistry, Chemical engineering, Specific surface area, General Materials Science, Texture (crystalline), Crystallite, 0210 nano-technology, Chemical composition, Stoichiometry
Abstract

International audience; The isothermal air heating (320 degrees C) of monolithic nanometric Ni1-xO (similar to 4 nm, 7% Ni3+) particles results in their sintering and concomitant loss of excess oxygen, leading to almost stoichiometric monolithic larger particles (similar to 7 nm, 0.5% Ni3+). By coupling crystallographic, thermal, textural and chemical analyses of the powders along heating, we could demonstrate that their evolutions in structure, texture and chemical composition are intimately linked and non-monotonous. First, while the particles/crystallites progressively coalesce and increase in size, their level of crystallographic strains increases until a saturation step in oxygen is reached (8 h). With time, this excess in oxygen is then progressively released, as well as the associated strains, and then the particles size and specific surface area stabilize (13 h). Beyond 13 h, the level of strains still monotonously decreases while a transient gain in oxygen/weight and a temporary decrease in crystallite size are observed before the final monolithic powder is produced (34 h). (C) 2016 Elsevier B.V. All rights reserved.

Published
2016

37. Electrochemical activity and high ionic conductivity of lithium copper pyroborate Li6CuB4O10

Author

Matthieu Saubanère, Daniel Alves Dalla Corte, Florian Strauss, Gwenaëlle Rousse, Mohamed Ben hassine, Matthieu Courty, Jean-Marie Tarascon, Robert Dominko, Hervé Vezin, Mingxue Tang, Université Pierre et Marie Curie - Paris 6 (UPMC), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Institute of Chemistry, Faculty of Chemistry and Chemical Technology, University of Ljubljana, 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), Laboratoire Structures, Propriétés et Modélisation des solides (SPMS), Institut de Chimie du CNRS (INC)-CentraleSupélec-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), 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), 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), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Univeristy of Ljubljana, 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 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 de Chimie du CNRS (INC)-Université de Lille-Centre National de la Recherche Scientifique (CNRS)-Centrale Lille Institut (CLIL), and Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Analytical chemistry, General Physics and Astronomy, chemistry.chemical_element, Context (language use), 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Redox, Copper, 0104 chemical sciences, law.invention, [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry, chemistry, law, Ionic conductivity, Lithium, Density functional theory, Physical and Theoretical Chemistry, 0210 nano-technology, Electron paramagnetic resonance
Abstract

In the search for new cathode materials for Li-ion batteries, borate (BO33-) based compounds have gained much interest during the last two decades due to the low molecular weight of the borate polyanions which leads to active materials with increased theoretical capacities. In this context we herein report the electrochemical activity versus lithium and the ionic conductivity of a diborate or pyroborate B2O54- based compound, Li6CuB4O10. By combining various electrochemical techniques with in situ X-ray diffraction, we show that this material can reversibly insert/deinsert limited amounts of lithium (~0.3 Li+) in a potential window ranging from 2.5 to 4.5 V vs. Li+/Li0. We demonstrate, via electron paramagnetic resonance (EPR), that such an electrochemical activity centered near 4.25 V vs. Li+/Li0 is associated with the Cu3+/Cu2+ redox couple, confirmed by density functional theory (DFT) calculations. Another specificity of this compound lies in its different electrochemical behavior when cycled down to 1 V vs. Li+/Li0 which leads to the extrusion of elemental copper via a conversion type reaction as deduced by transmission electron microscopy (TEM). Lastly, we probe the ionic conductivity by means of AC and DC impedance measurements as a function of temperature and show that Li6CuB4O10 undergoes a reversible structural transition around 350 °C, leading to a surprisingly high ionic conductivity of ~1.4 mS cm-1 at 500 °C.

Published
2016

38. Understanding the Formation of Soluble Bases in Nickel-Rich Layered Materials and Their Reactivity Towards Electrolyte

Author

Sylvie Grugeon, Pierre Tran-Van, Matthieu Courty, Ana Cristina Martinez, Stéphane Laruelle, Dominique Cailleu, and Bruno Delobel

Subjects
Nickel, Chemistry, Inorganic chemistry, chemistry.chemical_element, Reactivity (chemistry), Electrolyte
Abstract

In the last years, LiNixMnyCozO2 (x+y+z = 1) layered materials have been widely used as positive electrode materials in lithium-ion batteries for electric car applications, because of their high energy density given by the nickel content. Unfortunately, their stability towards H2O and CO2 is compromised when x>0.5, favoring the formation of surface species commonly called soluble bases (SB). The presence of SB has shown to increase the cell’s impedance, decrease the capacity retention and evolve gas during functioning1-4. Therefore, in this work, accurate SB quantification methods were implemented on four high-nickel layered materials with the aim of further deciphering their formation mechanisms and reactivity towards electrolyte. The optimization of a procedure that allows the quantification of SB in the as-received and after H2O/CO2storage of the NMC532, 622, 811 and LiNi0.9Co0.1O2, will be shown through the complementary use of acid-base titration and inductively coupled plasma (ICP) techniques. We unveiled the presence and quantified different lithium and sodium salts. Moreover, thanks to additional TGA/MS analysis, we propose a novel NMC surface degradation mechanism upon H2O/CO2 storage that involves the presence of lithium and nickel-based surface species. Finally, through nuclear magnetic resonance technique (19F and 31P NMR), the chemical reactivity of these surface species towards a commercial LiPF6-based liquid electrolyte was studied at room and at high temperature, evidencing the presence of lithium fluorophosphate as major decomposition product. 1. Liu, H. S., et al. (2006). "Investigation and improvement on the storage property of LiNi0.8Co0.2O2 as a cathode material for lithium-ion batteries." Journal of Power Sources 162(1): 644-650. 2. Bi, Y. J., et al. (2016). "Stability of Li2CO3 in cathode of lithium ion battery and its influence on electrochemical performance." Rsc Advances 6(23): 19233-19237. 3. Renfrew, S. E. and B. D. McCloskey (2017). "Residual Lithium Carbonate Predominantly Accounts for First Cycle CO2 and CO Outgassing of Li-Stoichiometric and Li-Rich Layered Transition-Metal Oxides." Journal of the American Chemical Society 139(49): 17853-17860. 4. Mahne, N., et al. (2018). "Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen." Angewandte Chemie-International Edition 57(19): 5529-5533.

Published
2020

39. Poly(Ethylene Oxide)−LiTFSI Solid Polymer Electrolyte Filaments for Fused Deposition Modeling Three-Dimensional Printing

Author

Sylvie Grugeon, Stéphane Panier, Hugues Tortajada, Matthieu Courty, Benoit Fleutot, Alexis Maurel, Loic Dupont, Carine Davoisne, and Michel Armand

Subjects
chemistry.chemical_classification, Materials science, Fused deposition modeling, Renewable Energy, Sustainability and the Environment, Oxide, Electrolyte, Polymer, Condensed Matter Physics, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, law.invention, chemistry.chemical_compound, Chemical engineering, chemistry, law, Three dimensional printing, Materials Chemistry, Electrochemistry, Poly ethylene
Abstract

Additive manufacturing technologies open the way to the direct-integration of electronics and solid-state battery within the final 3D object. Here, a 3D printable polyethylene oxide/lithium bis(trifluoromethanesulfonyl)imide (PEO/LiTFSI) filament (2.18 × 10−3 S cm−1 at 90 °C) optimized to be used as solid polymer electrolyte in a lithium-ion battery is produced to feed a fused deposition modeling (FDM) 3D-printer. Due to its relatively poor mechanical properties compared to classical polymer filament such as polylactic acid (PLA), deep modifications of the 3D-printer were implemented in order to facilitate its printability. The solid polymer electrolyte thermal, structural, morphological, mechanical and electrical characterization is reported. Interestingly, using three different electrochemical impedance spectroscopy sample holders (lateral, sandwich and interdigitated-comb), we demonstrate that conductivity values differs for a same sample, highlighting the PEO chains orientation effect on the conductivity measurements.

Published
2020

40. Temperature dependence of structural and transport properties for Na3V2(PO4)2F3 and Na3V2(PO4)2F2.5O0.5

Author

Philippe Veber, Annelise Brüll, François Fauth, Benoit Fleutot, Christian Masquelier, Rénald David, Laurence Croguennec, Thibault Broux, Matthieu Courty, Institut de Chimie de la Matière Condensée de Bordeaux (ICMCB), Université de Bordeaux (UB)-Institut Polytechnique de Bordeaux-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), European Synchrotron Radiation Facility (ESRF), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), the European Union’s Horizon 2020 research and innovation program under grant agreement No. 646433-NAIADES., ANR-10-LABX-0076,STORE-EX,Laboratory of excellency for electrochemical energy storage(2010), ANR-13-DESC-0001,SODIUM,Batteries à ions sodium pour des robots télécommandés(2013), Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), and Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)

Subjects
Electrode material, Phase transition, Valence (chemistry), Materials science, General Chemical Engineering, Analytical chemistry, chemistry.chemical_element, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 7. Clean energy, 01 natural sciences, Oxygen, 0104 chemical sciences, Ion, chemistry, Materials Chemistry, Fluorine, Ionic conductivity, 0210 nano-technology
Abstract

International audience; Among polyanionic-based electrode materials developed for Na-ion batteries, one of the most promising families turns out to be Na3V2(PO4)2F3–yOy (0 ≤ y ≤ 2). Here, we present the influence of the oxygen substitution for fluorine on the structural and transport properties of Na3V2(PO4)2F3–yOy, as a function of temperature, through the comparison of the two compositions y = 0 and y = 0.5. An order–disorder phase transition is observed, whatever the content in oxygen, in relation with changes in the ionic conductivity and thus with the mobility of the Na+ ions within the tunnels of the tridimensional structure. The richer the content in oxygen in Na3V2(PO4)2F3–yOy, the higher is the electronic conductivity, in relation with the mixed valence state V3+/V4+ within the bioctahedral units V2O8F3–yOy, and the better are the electrochemical performances in Na-ion batteries.

Published
2018

42. Synthesis of destabilized nanostructured lithium hydride via hydrogenation of lithium electrochemically inserted into graphite

Author

Claudia Zlotea, Liwu Huang, Jean-Pierre Bonnet, Michel Latroche, Matthieu Courty, Julie Bourgon, Luc Aymard, Franche-Comté Électronique Mécanique, Thermique et Optique - Sciences et Technologies (UMR 6174) (FEMTO-ST), Université de Technologie de Belfort-Montbeliard (UTBM)-Ecole Nationale Supérieure de Mécanique et des Microtechniques (ENSMM)-Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC)-Centre National de la Recherche Scientifique (CNRS), Groupe d'Etudes des Matériaux Hétérogènes (GEMH), Université de Limoges (UNILIM)-Institut des Procédés Appliqués aux Matériaux (IPAM), Université de Limoges (UNILIM)-Université de Limoges (UNILIM), Institut de Chimie et des Matériaux Paris-Est (ICMPE), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Centre interuniversitaire de recherche et d'ingenierie des matériaux (CIRIMAT), Centre National de la Recherche Scientifique (CNRS)-Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC), 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 Franche-Comté (UFC)-Centre National de la Recherche Scientifique (CNRS)-Ecole Nationale Supérieure de Mécanique et des Microtechniques (ENSMM)-Université de Technologie de Belfort-Montbeliard (UTBM), Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Université Fédérale Toulouse Midi-Pyrénées, Laboratoire réactivité et chimie des solides (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS), Université de Technologie de Belfort-Montbeliard (UTBM)-Ecole Nationale Supérieure de Mécanique et des Microtechniques (ENSMM)-Centre National de la Recherche Scientifique (CNRS)-Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC), Institut de Chimie du CNRS (INC)-Université Paris-Est Créteil Val-de-Marne - Paris 12 (UPEC UP12)-Centre National de la Recherche Scientifique (CNRS), Université Toulouse III - Paul Sabatier (UT3), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), and Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)

Subjects
Thermogravimetric analysis, Materials science, Renewable Energy, Sustainability and the Environment, Thermal decomposition, Intercalation (chemistry), Inorganic chemistry, Energy Engineering and Power Technology, chemistry.chemical_element, Condensed Matter Physics, chemistry.chemical_compound, Hydrogen storage, Fuel Technology, chemistry, Lithium hydride, Desorption, [CHIM]Chemical Sciences, Lithium, Graphite, ComputingMilieux_MISCELLANEOUS
Abstract

Lithium hydride-graphite composite is synthesized through hydrogenation of lithium intercalated graphite obtained by electrochemical insertion. XRD analysis indicates that the initial graphite is transformed into a mixture of LiC6 and LiC12 by the intercalation of 0.84 lithium for six carbons. After 20 h of hydrogenation under 30 bars at 150 °C, these lithium-inserted compounds are completely transformed into a lithium hydride-graphite composite based on the reaction: Li0.84C6 + 0.42H2 → 0.84LiH + 6C. A weak shift and broadening of the (002) reflex of graphite is observed after the formation of LiH, which is attributed to a small increase of the graphite disorder. Thermal gravimetric analysis coupled with Mass Spectrometry (TG-MS) shows that the desorption of this synthesized nano-LiH starts from around 200 °C, which is much lower than the decomposition temperature (900 °C) of pure LiH. It reveals that this new electrochemical synthesis process of LiH-graphite composites enables an interesting destabilization of the Li–H ionic bond due to a good dispersion of highly divided LiH nanoparticles (below 100 nm) in a carbon matrix. The hydrogen storage capacity of this LiH-graphite composite can be increased by subsequent Li insertion/hydrogenation cycles.

Published
2015

43. Discovery of a Sodium-Ordered Form of Na3V2(PO4)3 below Ambient Temperature

Author

Rénald David, Gwenaëlle Rousse, Olivier Mentré, Matthieu Courty, Christian Masquelier, and Jean-Noël Chotard

Subjects
Diffraction, Crystallography, Materials science, General Chemical Engineering, Phase (matter), Materials Chemistry, Fast ion conductor, General Chemistry, Crystal structure, Atmospheric temperature range, Single crystal, Powder diffraction, Monoclinic crystal system
Abstract

The crystal structure of the NASICON Na3V2(PO4)3 phase (NVP) has been investigated as a function of temperature. Combining laboratory and synchrotron X-ray powder diffraction with single crystal X-ray diffraction, we demonstrate the presence of four polymorphs of NVP from 30 to 225 °C. While the high temperature γ-NVP crystallizes in the classical rhombohedral cell (S.G. R3c, a = 8.73382(4) A, c = 21.91438(17) A), the low temperature α-NVP undergoes a monoclinic distortion (S.G. C2/c, a = 15.1244(6) A, b = 8.7287(3) A, c = 21.6143(8) A, β = 90.163(2)°) together with an ordering of the Na atoms. In the middle temperature range, two incommensurate modulated structures (β- and β′-NVP) are also reported for the first time.

Published
2015

44. Improving the energy density of Na3V2(PO4)3-based positive electrodes through V/Al substitution

Author

Rénald David, Vincent Seznec, Matthieu Courty, Jean-Noël Chotard, Fabien Lalère, and Christian Masquelier

Subjects
Phase transition, Renewable Energy, Sustainability and the Environment, Crystal chemistry, Chemistry, Vanadium, chemistry.chemical_element, General Chemistry, Electrochemistry, Redox, Ion, Crystallography, Fast ion conductor, General Materials Science, Monoclinic crystal system
Abstract

The crystal chemistry and the electrochemical properties upon Na+ extraction/insertion of NASICON-type Na3AlyV2−y(PO4)3 compositions (y = 0.1, 0.25 and 0.5) were investigated. It was found that this family of V/Al substituted NASICON materials undergoes multiple reversible phase transitions between −50 °C and 250 °C upon heating, from monoclinic to rhombohedral symmetry, related to progressive disordering of Na+ ions within the framework. Na+ insertion/extraction mechanisms were monitored by operando X-ray diffraction. It is shown for the first time that substitution of aluminum for vanadium in Na3Al0.5V1.5(PO4)3 increases significantly the theoretical energy density of these promising positive electrodes (425 W h kg−1) due to its lighter molecular weight and the possibility of reversible operation on the V4+/V5+ redox couple at 3.95 V vs. Na+/Na.

Published
2015

45. Partially Oxidized Silicon Particles for Stable Aqueous Slurries and Practical Large-Scale Making of Si-Based Electrodes

Author

Nicolas Mariage, Matthieu Courty, Mathieu Morcrette, Amina Touidjine, Dominique Larcher, Michael Lejeune, Willy Porcher, and Carine Davoisne

Subjects
Materials science, Aqueous solution, Scale (ratio), Silicon, Renewable Energy, Sustainability and the Environment, Metallurgy, chemistry.chemical_element, Condensed Matter Physics, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Electrode, Materials Chemistry, Electrochemistry, Slurry
Published
2015

46. Polymorphism in Bi2(SO4)3

Author

Philippe Barboux, Matthieu Courty, Chinmayee V. Subban, Gwenaëlle Rousse, and Jean-Marie Tarascon

Subjects
Crystallography, Materials science, Polymorphism (materials science), General Materials Science, General Chemistry, Crystal structure, Condensed Matter Physics, Powder diffraction, Layered structure
Abstract

A new polymorph of Bi 2 (SO 4 ) 3 was prepared by reaction of LiBiO 2 with H 2 SO 4 and its crystal structure was solved from X-ray powder diffraction. This new polymorph crystallizes in C 2/ c space group with lattice parameters a = 17.3383(3) A, b = 6.77803(12) A, c = 8.30978(13) A, β = 101.4300(12)°. Bi 2 (SO 4 ) 3 presents a layered structure made of SO 4 sulfate groups and signs of stereochemically active Bi 3+ lone pairs. The new Bi 2 (SO 4 ) 3 absorbs water to form Bi 2 (H 2 O) 2 (SO 4 ) 2 (OH) 2 through an intermediate Bi 2 O(OH) 2 SO 4 phase, and the transition is reversible when heated under vacuum.

Published
2014

47. Synthesis, Structure, and Electrochemical Properties of Na

Author

Florian, Strauss, Gwenaëlle, Rousse, Moulay Tahar, Sougrati, Daniel Alves, Dalla Corte, Matthieu, Courty, Robert, Dominko, and Jean-Marie, Tarascon

Abstract

In the search for new cathode materials for sodium ion batteries, the exploration of polyanionic compounds has led to attractive candidates in terms of high redox potential and cycling stability. Herein we report the synthesis of the two new sodium transition-metal pentaborates Na

Published
2016

48. Synthesis, Structure, and Electrochemical Properties of Na3MB5O10 (M = Fe, Co) Containing M2+in Tetrahedral Coordination

Author

Gwenaëlle Rousse, Daniel Alves Dalla Corte, Robert Dominko, Florian Strauss, Jean-Marie Tarascon, Matthieu Courty, Moulay Tahar Sougrati, Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), National Institute of Chemistry, Université Pierre et Marie Curie - Paris 6 (UPMC), 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), 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), 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 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), and Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)

Subjects
Diffraction, Chemistry, Sodium, Inorganic chemistry, chemistry.chemical_element, 02 engineering and technology, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, Redox, Synchrotron, Cathode, 0104 chemical sciences, law.invention, Inorganic Chemistry, Crystallography, law, Mössbauer spectroscopy, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, 0210 nano-technology, Boron
Abstract

International audience; In the search for new cathode materials for sodium ion batteries, the exploration of polyanionic compounds has led to attractive candidates in terms of high redox potential and cycling stability. Herein we report the synthesis of two new sodium transition metal pentaborates Na 3 MB 5 O 10 (M = Fe, Co), where Na 3 FeB 5 O 10 represents the first sodium iron borate reported at present. By means of synchrotron X-ray diffraction, we reveal a layered structure consisting of pentaborate B 5 O 10 groups connected through M 2+ in tetrahedral coordination, providing possible three-dimensional Na-ion migration pathways. Inspired by these structural features we examined the electrochemical performances versus sodium and show that Na 3 FeB 5 O 10 is active at an average potential of 2.5 V vs. Na + /Na 0 , correlated to the Fe 3+ /Fe 2+ redox couple as deduced from ex situ Mössbauer measurements. This contrasts with Na 3 CoB 5 O 10 which is electrochemical inactive. Moreover, we show that their electrochemical performances are kinetically limited as deduced by complementary AC/DC conductivity measurements, hence confirming once again the complexity in designing highly performant borate-based electrodes.

Published
2016

49. Iron Phosphate/Bacteria Composites as Precursors for Textured Electrode Materials with Enhanced Electrochemical Properties

Author

Samuel Bernard, Moulay Tahar Sougrati, Olivier Beyssac, Carine Davoisne, Nadir Recham, François Guyot, Dominique Larcher, Jean-Marie Tarascon, Arnaud Demortière, Jennyfer Miot, Boris Mirvaux, Matthieu Courty, 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), 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), 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), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), 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), 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)-Institut de recherche pour le développement [IRD] : UR206-Muséum national d'Histoire naturelle (MNHN)-Centre National de la Recherche Scientifique (CNRS), 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, 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, Materials science, biology, Renewable Energy, Sustainability and the Environment, Inorganic chemistry, 02 engineering and technology, [CHIM.MATE]Chemical Sciences/Material chemistry, 010502 geochemistry & geophysics, 021001 nanoscience & nanotechnology, Condensed Matter Physics, biology.organism_classification, Electrochemistry, 01 natural sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Chemical engineering, Materials Chemistry, Iron phosphate, 0210 nano-technology, Bacteria, ComputingMilieux_MISCELLANEOUS, 0105 earth and related environmental sciences
Abstract

International audience

Published
2016

50. Highly Loaded Graphite Composite PLA-Based Filaments for Lithium-Ion Battery 3D-Printing

Author

Alexis Maurel, Matthieu Courty, Benoit Fleutot, Hugues Tortajada, Kalappa Prashantha, Michel Armand, Sylvie Grugeon, Stéphane Panier, and Loic Dupont

Abstract

Actual parallel-plate architecture of lithium-ion batteries consists in lithium ion diffusion in one dimension between the electrodes. To achieve higher performances in terms of specific capacity and power, configurations enabling lithium ion diffusion in two or three dimensions have been considered (1-5). With a view to build these complex 3D battery architectures avoiding the electrodes interpenetration issues, this work was focused on the Fused Deposition Modeling (FDM). In this presentation, the formulation and characterization of a 3D-printing graphite/polylactic-acid (PLA) filament, specially designed to be used as negative electrode in a lithium-ion battery, and to feed a conventional FDM 3D-printer will be described (6). Graphite loading into the produced filament was increased as high as possible (up to 62.5%wt) to enhance the electrochemical performances while maintaining sufficient mechanical strength to be printed. Formulation process is displayed in Fig. 1a. With such a high ratio of active material, the graphite/PLA filament was found to be very brittle. To overcome this problem, a plasticizer has been added to the PLA matrix to improve its ductility and decrease its stiffness. Influence of the amount of various plasticizers such as propylene carbonate (PC), poly(ethylene glycol) dimethyl ether average Mn~2000 (PEGDME2000), poly(ethylene glycol) dimethyl ether average Mn~500 (PEGDME500) and acetyl tributyl citrate (ATBC) was investigated by performing both differential scanning calorimetry and tensile mechanical tests. On the other hand, printability behavior of the extruded composite filaments was tested by using a commercially available 3D printer. From the optimized plasticizer composition, two-dimensional discs but also high resolution complex three-dimensional structures, such as a semi-cube lattice and a “3Dbenchy” boat, were successfully 3D-printed. Finally, considering this optimized composite, an in-depth study was carried out to identify the electronic percolation (Fig. 1b) and electrochemical impact of carbon black SuperP and carbon nanofibers as conductive additives; electrical conductivities were determined from impedance measurements performed at various stabilized temperatures ranging from 20ºC to 50°C and, in parallel, capacity retention was investigated in detail at different current densities after the different elaboration steps (film before extrusion and disc after printing). Significant progress has been achieved regarding the capacity retention as compared to Foster et al. (7) who was the first group to use FDM technology to 3D-print a negative electrode disc. They were aware that the low specific capacity values reported (15.8 mAh.g-1 at current density of 10 mA.g-1) were unfortunately caused by the use of a filament containing only 8%wt of graphene as active material and 92%wt of PLA. In this work, by increasing the graphite loading up to 62.5%wt, a reversible capacity of 201 mAh.g- 1 at current density of 4 mA.g-1 was achieved for the 3D-printed negative electrode disc by using the most printable filament (Fig. 1c). References: J. W. Long, B. Dunn, D. R. Rolison and H. S. White, Chemical Reviews, 104, 4463 (2004). S. Ferrari, M. Loveridge, S. D. Beattie, M. Jahn, R. J. Dashwood and R. Bhagat, Journal of Power Sources, 286, 25 (2015). H. S. Min, B. Y. Park, L. Taherabadi, C. L. Wang, Y. Yeh, R. Zaouk, M. J. Madou and B. Dunn, Journal of Power Sources, 178, 795 (2008). L. Taberna, S. Mitra, P. Poizot, P. Simon and J. M. Tarascon, Nature Materials, 5, 567 (2006). K. Sun, T. S. Wei, B. Y. Ahn, J. Y. Seo, S. J. Dillon and J. A. Lewis, Advanced Materials, 25, 4539 (2013). A. Maurel, M. Courty, B. Fleutot, H. Tortajada, K. Prashantha, M. Armand, S. Grugeon, S. Panier and L. Dupont, Advanced Energy Materials, (submitted April 2018). C. W. Foster, M. P. Down, Y. Zhang, X. B. Ji, S. J. Rowley-Neale, G. C. Smith, P. J. Kelly and C. E. Banks, Scientific Reports, 7 (2017). Figure 1

Published
2018

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