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1. 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

2. 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

3. 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

4. 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

5. 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

6. 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

7. 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

8. 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

9. 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

10. 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

11. 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

12. 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

13. 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

14. 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

15. 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

16. 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

17. 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

18. 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

19. An Oxysulfate Fe2O(SO4)2 Electrode for Sustainable Li-Based Batteries

Author: Marie-Liesse Doublet, Moulay Tahar Sougrati, Artem M. Abakumov, Matthieu Courty, Gwenaëlle Rousse, Gustaaf Van Tendeloo, Meiling Sun, Jean-Marie Tarascon, Réseau sur le stockage électrochimique de l'énergie (RS2E), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Université Pierre et Marie Curie - Paris 6 (UPMC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Collège de France - Chaire Chimie du solide et énergie, Chimie du solide et de l'énergie (CSE), Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), RS2E, Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Aix Marseille Université (AMU)-Université de Pau et des Pays de l'Adour (UPPA)-Université de Nantes (UN)-Université de Montpellier (UM)-Centre National de la Recherche Scientifique (CNRS)-Sorbonne Université (SU)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université Fédérale Toulouse Midi-Pyrénées-Université Fédérale Toulouse Midi-Pyrénées-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Chaire Chimie du solide et énergie, and Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Sorbonne Université (SU)
Subjects: Electrode material, Chemistry, Inorganic chemistry, Nanotechnology, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, 7. Clean energy, 01 natural sciences, Biochemistry, Redox, Catalysis, 0104 chemical sciences, Colloid and Surface Chemistry, Octahedron, Phase (matter), Electrode, [PHYS.COND.CM-MS]Physics [physics]/Condensed Matter [cond-mat]/Materials Science [cond-mat.mtrl-sci], 0210 nano-technology
Abstract: International audience; High-performing Fe-based electrodes for Li-based batteries are eagerly pursued because of the abundance and environmental benignity of iron, with especially great interest in polyanionic compounds because of their flexibility in tuning the Fe3+/Fe2+ redox potential. We report herein the synthesis and structure of a new Fe-based oxysulfate phase, Fe2O(SO4)2, made at low temperature from abundant elements, which electrochemically reacts with nearly 1.6 Li atoms at an average voltage of 3.0 V versus Li+/Li, leading to a sustained reversible capacity of ≈125 mAh/g. The Li insertion–deinsertion process, the first ever reported in any oxysulfate, entails complex phase transformations associated with the position of iron within the FeO6 octahedra. This finding opens a new path worth exploring in the quest for new positive electrode materials.
Published: 2014

20. Biomass derived ionic liquids: synthesis from natural organic acids, characterization, toxicity, biodegradation and use as solvents for catalytic hydrogenation processes

Author: Annette Haiß, Brid Quilty, Sandrine Bouquillon, Sylvain Gatard, Matthieu Courty, Nadège Ferlin, Ian Beadham, Nicholas Gathergood, Marcel Špulák, Klaus Kümmerer, Mukund Ghavre, Institut de Chimie Moléculaire de Reims - UMR 7312 (ICMR), SFR Condorcet, Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-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), Université de Reims Champagne-Ardenne (URCA), Department of Inorganic and Organic Chemistry, Charles University [Prague] (CU), School of Biotechnology and National Institute for Cellular Biotechnology, Dublin City University [Dublin] (DCU), School of Chemical Sciences and National Institute for Cellular Biotechnology, Institute of Sustainable and Environmental Chemistry, and Leuphana University Lüneburg
Subjects: Thermogravimetric analysis, Glucuronate, Characterization, Tartrate, 010402 general chemistry, Sustainability Science, 01 natural sciences, Biochemistry, Synthesis, chemistry.chemical_compound, Cyclooctene, Drug Discovery, Organic chemistry, Biology, Toxicity, [CHIM.ORGA]Chemical Sciences/Organic chemistry, 010405 organic chemistry, Chemistry, Tetrabutylammonium hydroxide, Organic Chemistry, Biodegradation, 6. Clean water, Ionic liquids, 0104 chemical sciences, Malonate, Ionic liquid, Hydrogenation
Abstract: International audience; Ionic liquids with natural organic derived anions (L-lactate, L-tartrate, malonate, succinate, L-malate, pyruvate,D-glucuronate, D-galacturonate) were easily prepared from tetrabutylammonium hydroxide and an excess of the corresponding acid with good yields. Their characterization was realized through classical NMR, IR, and elemental analysis techniques; their viscosity and TGA (thermogravimetric analysis) parameters were also determined. These ionic liquids showed good performance and recyclability in the selective catalytic hydrogenation of 1,5-cyclooctadiene (1,5-COD) into cyclooctene (COD) at room temperature under atmospheric H2pressure. Antimicrobial toxicity assays toward a large panel of bacteria and fungi strains were also completed and biodegradation studies (Closed Bottle test, 28 days) were also performed.
Published: 2013

21. A new sensitive organic/inorganic hybrid material based on titanium oxide for the potentiometric detection of iron(III)

Author: Pascal Rouge, Christel Gervais, Pascal Sonnet, Matthieu Becuwe, Alexandra Dassonville-Klimpt, Matthieu Courty, E. Baudrin, Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Centre National de la Recherche Scientifique (CNRS)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)
Subjects: Magnetic Resonance Spectroscopy, Materials science, Surface Properties, Iron, Inorganic chemistry, Potentiometric titration, Oxide, 02 engineering and technology, 010402 general chemistry, Potentiometric detection, 01 natural sciences, Biomaterials, chemistry.chemical_compound, Colloid and Surface Chemistry, Microscopy, Electron, Transmission, X-Ray Diffraction, Spectroscopy, Fourier Transform Infrared, Fourier transform infrared spectroscopy, Thermal analysis, Hybrid material, Titanium, Titanium oxide, Organophosphorous coupling agent, Substrate (chemistry), [CHIM.MATE]Chemical Sciences/Material chemistry, Iron(III), 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Titanium dioxide, Potentiometry, 0210 nano-technology
Abstract: International audience; The formation of a new hybrid material based on titanium dioxide as inorganic support and containing an iron organochelator (ICL670) is described. An organophosphorous coupling agent was used to graft the organic molecule on the oxide surface. The attachment of the organic substrate was well-confirmed by FTIR (DRIFT), solid-state 31P and 13C CPMAS NMR, thermal analysis and the integrity of the structural and morphological parameters were verified using XRD and TEM analyses. The interaction between the material and dissolved iron(III) was also investigated through potentiometric measurements and demonstrated the interest of this new non-siliceous based hybrid material. The obtained linear evolution of the open circuit potential from 10−2 to 10−6 mol L−1 can be used for the analytical detection of iron(III).
Published: 2012

22. 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

23. Ionothermal Synthesis of Tailor-Made LiFePO4 Powders for Li-Ion Battery Applications

Author: Michel Armand, Matthieu Courty, Loic Dupont, Nadir Recham, Dominique Larcher, Jean-Marie Tarascon, and Karim Djellab
Subjects: Battery (electricity), Materials science, General Chemical Engineering, Inorganic chemistry, chemistry.chemical_element, Crystal growth, 02 engineering and technology, General Chemistry, 010402 general chemistry, 021001 nanoscience & nanotechnology, Electrochemistry, 01 natural sciences, 0104 chemical sciences, Ion, Solvent, chemistry.chemical_compound, chemistry, Chemical engineering, visual_art, Ionic liquid, Materials Chemistry, visual_art.visual_art_medium, Lithium, Ceramic, 0210 nano-technology
Abstract: As opposed to ceramic methods, low-temperature solvothermal-hydrothermal methods using liquid media as reaction support are less energy demanding to design new electrode materials; therefore, they tend to replace ceramic routes. Here, we report the use of ionic liquids as both solvent and template to enable the growth of LiFePO4 (LFP) powders with controlled size and morphology at temperatures at least 200 °C lower than those required for conventional ceramic methods, while showing excellent electrochemical performances versus lithium. An inherent advantage to the use of ionic liquids lies in the feasibility of carrying out the reaction at atmospheric pressure. Besides, the recovery of the powders from the reacting medium is particularly easy, as are the effluents and ionic liquid recycling. Additionally, it is shown that ionic liquids can be used as a structural directing agent to orient crystal growth and obtain powders adopting a single morphology. Needless to say, such a new approach, which is not spe...
Published: 2009

24. Tetrabutylammonium prolinate-based ionic liquids:A combined asymmetric catalysis, antimicrobial toxicity and biodegradation assessment

Author: Nadège Ferlin, Annette Haiß, Sandrine Bouquillon, Milan Pour, Brid Quilty, Sylvain Gatard, Albert Nguyen Van Nhien, Matthieu Courty, Nicholas Gathergood, Klaus Kümmerer, Mukund Ghavre, Institut de Chimie Moléculaire de Reims - UMR 7312 (ICMR), SFR Condorcet, Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-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), Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), and Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Chiral ionic liquids, Double bond, Enantioselective hydrogenation, General Chemical Engineering, Carbon-carbon double bonds, Decomposition temperature, One-Step, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Asymmetric catalysis, Unsaturated ketones, Organic chemistry, [CHIM]Chemical Sciences, Closed bottle biodegradation tests, chemistry.chemical_classification, 010405 organic chemistry, Chemistry, Tetrabutylammonium hydroxide, Thermal decomposition, Enantioselective synthesis, Tetrabutylammonium hydroxides, General Chemistry, Biodegradation, Antimicrobial, 0104 chemical sciences, Ionic liquid
Abstract: International audience; Chiral ionic liquids (CILs) tetrabutylammonium-(S)-prolinate, tetrabutylammonium-(R)-prolinate and tetrabutylammonium trans-4-hydroxy-(S)-prolinate were investigated as chiral additives in the Pd-catalyzed enantioselective hydrogenation of α,β-unsaturated ketones. These CILs were easily prepared in one step from the aminoacid and tetrabutylammonium hydroxide and characterized (NMR, IR, optical rotation, elemental analysis, DSC, viscosity, decomposition temperature). The research strategy was to assess the antimicrobial toxicity (>20 strains) and biodegradability (OECD 301D) of the CILs at the same time as undertaking the asymmetric catalysis study. The Pd-catalyzed enantioselective hydrogenation of the carbon–carbon double bond of α,β-unsaturated ketones under mild conditions (room temperature, 1 atm of H2) in different solvents with CILs present. The best results were obtained in i-PrOH after 18 hours of reaction with a i-PrOH/IL ratio of 5. While all three CILs have low antimicrobial toxicity to a wide range of bacteria and fungi, tetrabutylammonium-(S)-prolinate, tetrabutylammonium-(R)-prolinate and tetrabutylammonium trans-4-hydroxy-(S)-prolinate did not pass the Closed Bottle biodegradation test.
Published: 2013

25. Click Reactions as a Key Step for an Efficient and Selective Synthesis of D-Xylose-Based ILs

Author: Sylvain Gatard, Albert Nguyen Van Nhien, Nadège Ferlin, Sandrine Bouquillon, Matthieu Courty, Institut de Chimie Moléculaire de Reims - UMR 7312 (ICMR), SFR Condorcet, Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), 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: ionic liquids, D-xylose, click chemistry, Pharmaceutical Science, Xylose, 010402 general chemistry, Mass spectrometry, 01 natural sciences, Methylation, TP Chemical technology, Catalysis, Article, Analytical Chemistry, lcsh:QD241-441, chemistry.chemical_compound, Reaction sequence, Drug Stability, lcsh:Organic chemistry, Drug Discovery, Organic chemistry, [CHIM]Chemical Sciences, Physical and Theoretical Chemistry, Cycloaddition Reaction, 010405 organic chemistry, Chemistry, Organic Chemistry, Cycloaddition, 0104 chemical sciences, Chemistry (miscellaneous), Elemental analysis, Ionic liquid, Thermogravimetry, Click chemistry, Molecular Medicine, Copper
Abstract: International audience; D-Xylose-based ionic liquids have been prepared from D-xylose following a five steps reaction sequence, the key step being a click cycloaddition. These ionic liquids (ILs) have been characterized through classical analytical methods (IR, NMR, mass spectroscopy, elemental analysis) and their stability constants, Tg and Tdec, were also determined. Considering their properties and their hydrophilicity, these compounds could be alternative solvents for chemical applications under mild conditions.
Published: 2013

26. Preparation and characterization of LiNi0.5Mn1.5O4−δ thin films taking advantage of correlations with powder samples behavior

Author: Emmanuel Baudrin, Matthieu Courty, Liping Wang, Hong Li, Xuejie Huang, Beijing National Laboratory for Condensed Matter Physics, Chinese Academy of Sciences [Beijing] (CAS), 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), Laboratoire de Glycochimie, des Antimicrobiens et des Agro-ressources - UMR CNRS 7378 (LG2A ), and Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Materials science, Renewable Energy, Sustainability and the Environment, Annealing (metallurgy), [SDV]Life Sciences [q-bio], Spinel, Analytical chemistry, Energy Engineering and Power Technology, chemistry.chemical_element, 02 engineering and technology, Electrolyte, engineering.material, 010402 general chemistry, 021001 nanoscience & nanotechnology, Microstructure, 01 natural sciences, Oxygen, 0104 chemical sciences, Pulsed laser deposition, chemistry, engineering, Electrical and Electronic Engineering, Physical and Theoretical Chemistry, Thin film, 0210 nano-technology, Stoichiometry
Abstract: International audience; The high voltage spinel LiNi0.5Mn1.5O 4-δ films were obtained by pulsed laser deposition. The effects of oxygen deficiency, annealing treatment, and film thickness on microstructure, morphology and electrochemical properties were investigated. We showed that tuning the oxygen pressure and annealing treatment allows modifying the oxygen film stoichiometry. Trying to determine the oxygen stoichiometry in thin films, a series of oxygen-deficient spinel "LiNi0.5Mn 1.5O4-δ" powder samples by quench steps from different temperatures were prepared. It is demonstrated that powders and thin films presenting similar cell parameters, namely related to the oxygen stoichiometry, show similar electrochemical profiles. Meanwhile, the compatibility of electrolyte with substrate and the stability of the target were also investigated.
Published: 2013

27. Syntheses and characterisation of hydrophobic ionic liquids containing trialkyl(2-ethoxy-2-oxoethyl)ammonium or N-(1-methylpyrrolidyl-2-ethoxy-2-oxoethyl)ammonium cations

Author: Patrick Fricoteaux, Matthieu Courty, Albert Nguyen-Van-Nhien, Aminou Mohamadou, Stéphanie Boudesocque, Ahmed Messadi, Laurent Dupont, Institut de Chimie Moléculaire de Reims - UMR 7312 (ICMR), SFR Condorcet, Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Laboratoire d'ingénierie des systèmes macromoléculaires (LISM), Centre National de la Recherche Scientifique (CNRS)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Aix Marseille Université (AMU), Laboratoire des Glucides (LG), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-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)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Centre National de la Recherche Scientifique (CNRS), Aix Marseille Université (AMU)-Institut National de la Santé et de la Recherche Médicale (INSERM)-Centre National de la Recherche Scientifique (CNRS), Laboratoire réactivité et chimie des solides (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS), Université de Reims Champagne-Ardenne (URCA)-Institut de Chimie du CNRS (INC)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), Université de Reims Champagne-Ardenne (URCA)-Université de Reims Champagne-Ardenne (URCA)-Centre National de la Recherche Scientifique (CNRS)-SFR Condorcet, Université de Reims Champagne-Ardenne (URCA)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-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 Reims Champagne-Ardenne (URCA)-SFR CAP Santé (Champagne-Ardenne Picardie Santé), Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-SFR Condorcet, and Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Université de Reims Champagne-Ardenne (URCA)-Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Tetrafluoroborate, Bis(trifluoromethylsulfonyl)imide, [CHIM.INOR]Chemical Sciences/Inorganic chemistry, 010402 general chemistry, 01 natural sciences, chemistry.chemical_compound, Glycine-betaine, Polymer chemistry, Materials Chemistry, Organic chemistry, Ammonium, [CHIM.COOR]Chemical Sciences/Coordination chemistry, Physical and Theoretical Chemistry, Imide, Dicyanamide, Spectroscopy, Alkyl, ComputingMilieux_MISCELLANEOUS, chemistry.chemical_classification, 010405 organic chemistry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, Hydrophobic ionic liquid, Condensed Matter Physics, Atomic and Molecular Physics, and Optics, 0104 chemical sciences, Electronic, Optical and Magnetic Materials, chemistry, Ionic liquid, Alkoxy group, Electrochemical window
Abstract: International audience; A series of salts based on ethyl ester betaine derivatives [trialkyl(2-ethoxy-2-oxoethyl)ammonium or N-(1-methylpyrrolidyl-2-ethoxy-2-oxoethyl)ammonium cations] with alkyl chains [ethyl, n-propyl and n-butyl] have been synthesized. These cations generate hydrophobic ionic liquids with bis(trifluoromethylsulfonyl)imide, tetrafluoroborate or dicyanamide anions. The influence of the alkyl chain length and the chemical nature of the counteranion on physicochemical properties such as density, melting point, glass transition and decomposition temperatures, viscosity, and electrochemical window have been investigated.
Published: 2013

28. A green Li-organic battery working as a fuel cell in case of emergency

Author: Philippe Poizot, Anne-Lise Barrès, Sébastien Gottis, Olivier Chauvet, Matthieu Courty, Stéven Renault, Franck Dolhem, 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), Laboratoire des Glucides (LG), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Picardie Jules Verne (UPJV), Institut des Matériaux Jean Rouxel (IMN), Université de Nantes - UFR des Sciences et des Techniques (UN UFR ST), Université de Nantes (UN)-Université de Nantes (UN)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Ecole Polytechnique de l'Université de Nantes (EPUN), Université de Nantes (UN)-Université de Nantes (UN), GCEP program from Stanford University and the Région Picardie and the FEDER program, Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Université de Nantes (UN)-Aix Marseille Université (AMU)-Université de Haute-Alsace (UHA) Mulhouse - Colmar (Université de Haute-Alsace (UHA))-Collège de France (CdF (institution))-Université de Picardie Jules Verne (UPJV)-Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université de Pau et des Pays de l'Adour (UPPA)-Institut de Chimie du CNRS (INC)-Université de Montpellier (UM)-Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS)-Institut National Polytechnique (Toulouse) (Toulouse INP), Université de Toulouse (UT)-Université de Toulouse (UT)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Université Grenoble Alpes (UGA), Université de Nantes (UN)-Université de Nantes (UN)-Ecole Polytechnique de l'Université de Nantes (EPUN), and Université de Nantes (UN)-Université de Nantes (UN)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Battery (electricity), Engineering, Chemical substance, Organic radical battery, Nanotechnology, Context (language use), 02 engineering and technology, 010402 general chemistry, Electrochemistry, 7. Clean energy, 01 natural sciences, self-recharging, 12. Responsible consumption, 5-dilithium-oxy)-terephthalate salt, Li battery, Environmental Chemistry, Process engineering, Retrosynthetic analysis, oxygen scavenger, LiO2, Renewable Energy, Sustainability and the Environment, business.industry, [CHIM.ORGA]Chemical Sciences/Organic chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Pollution, organic electrode, 0104 chemical sciences, Nuclear Energy and Engineering, dilithium (2, Electricity, Electric power, 0210 nano-technology, business
Abstract: International audience; The routine access to electricity always means a drastic change in terms of quality of life making it easierand safer. Consequently, the global electric demand both on and off-the-grid is growing and calls for ongoing innovation to promote reliable, clean and safe power supplies. In this context, the development of new chemistries for batteries and fuel cells could play a critical role. From our prospects aiming at fostering the concept of sustainable organic batteries, we report in this article on the peculiar properties of dilithium (2,5-dilithium-oxy)-terephthalate salt, a novel redox-active material. Based on an oriented retrosynthetic analysis, we have succeeded in elaborating this organic electrode material through an original and low-polluting synthesis scheme, which includes both chemical and biochemical CO2 sequestration in conjunction with a closed-loop solution for recycling products. Beyond its remarkable electrochemical performance vs. Li, especially as a lithiated cathode material, this compound behaves also like an oxygen scavenger. This dual electrochemical/chemical reactivity makes the self-recharging of a Li cell based on this organic salt possible by opening it to air ensuring an electrical power reserve when a conventional electrical recharge is not possible. In such a case, the pristine rechargeable Li-organic battery operates as a sort of "Li/O2 fuel cell".
Published: 2013

29. Calix[4]arene-modified silica nanoparticles for the potentiometric detection of iron (III) in aqueous solution

Author: Pascal Sonnet, Dominique Cailleu, Christel Gervais, Pascal Rouge, Matthieu Becuwe, Alexandra Dassonville-Klimpt, Matthieu Courty, E. Baudrin, 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), Laboratoire des Glucides (LG), Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université de Picardie Jules Verne (UPJV), Spectroscopie, Modélisation, Interfaces pour L'Environnement et la Santé (SMiLES), Laboratoire de Chimie de la Matière Condensée de Paris (LCMCP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Collège de France (CdF (institution))-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), and Université de Picardie Jules Verne (UPJV)-Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)
Subjects: Aqueous solution, Chemistry, Ligand, General Chemical Engineering, 010401 analytical chemistry, Potentiometric titration, Inorganic chemistry, 02 engineering and technology, General Chemistry, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, Coupling reaction, Calix[4]arene, 0104 chemical sciences, Nucleophile, Covalent bond, Potentiometry, ICL670, Fourier transform infrared spectroscopy, 0210 nano-technology, Hybrid material, Iron sensor
Abstract: International audience; This article aims to present the synthesis and the characterization of a novel hybrid material, based on silica nanoparticles, and which can be used as a sensitive element for the electrochemical detection of iron (III). This material was obtained by grafting an iron ligand-based calix[4]arene structure onto nanosized silica particles. The covalent anchoring of the chelator was obtained by nucleophilic coupling reaction between the modified calix[4]arene and the chloropropyl functionalized silica. The grafting reaction was confirmed by FTIR (DRIFT), solid-state 13C Cross-Polarization MAS (CPMAS) NMR and thermal analysis. The interaction between the material and the dissolved iron (III) was demonstrated though potentiometric measurements. A linear evolution of the open circuit potential, which can be used analytically for iron (III) detection, has been obtained.
Published: 2012

30. Single-ion polymer electrolytes based on a delocalized polyanion for lithium batteries

Author: Rachid Meziane, Karim Djellab, Matthieu Courty, Jean-Pierre Bonnet, Michel Armand, 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: chemistry.chemical_classification, General Chemical Engineering, Radical polymerization, Analytical chemistry, chemistry.chemical_element, Ionic bonding, 02 engineering and technology, Polymer, 010402 general chemistry, 021001 nanoscience & nanotechnology, 01 natural sciences, 7. Clean energy, Polyelectrolyte, 0104 chemical sciences, chemistry, Chemical engineering, Electrochemistry, Fast ion conductor, Ionic conductivity, [CHIM]Chemical Sciences, Lithium, 0210 nano-technology, Lithium Cation
Abstract: Lithium poly(4-styrenesulfonyl(trifluoromethylsulfonyl)imide) (PSTFSI) polyelectrolytes made up of SO 2 N − SO 2 CF 3 anionic groups associated with a lithium cation and attached to a polystyrene chain have been prepared. In these polymers the transference number of the lithium cation is expected to be unity while the ionic conductivity is kept high. Two different single-ion polymers with a similar final structure were synthesized by two ways, monomer free radical polymerization and polymer modification (PSTFSI (a) and PSTFSI (b), respectively). These polyelectrolytes were mixed with poly(ethylene oxide) PEO into a composite membrane to form solid electrolytes for lithium batteries. These polymer alloys were studied by scanning electron microscopy (SEM), thermal analysis and impedance spectroscopy to measure the ionic transport properties. Interestingly, ionic conductivity is about ten times higher for a membrane with PSTFSI (a) (≈10 −5 S cm −1 ) compared to a membrane with lithium poly(styrene sulfonate) or with PSTFSI (b) above PEO melting temperature.
Published: 2011

31. Fluorosulfate Positive Electrodes for Li-Ion Batteries Made via a Solid-State Dry Process

Author: Jean-Marie Tarascon, Jean-Claude Jumas, Moulay Tahar Sougrati, M. Ati, Jean-Bernard Leriche, Nadir Recham, Prabeer Barpanda, Matthieu Courty, Michel Armand, Laboratoire réactivité et chimie des solides - UMR CNRS 7314 (LRCS), Université de Picardie Jules Verne (UPJV)-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC), Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier (ICGM ICMMM), Ecole Nationale Supérieure de Chimie de Montpellier (ENSCM)-Centre National de la Recherche Scientifique (CNRS)-Université de Montpellier (UM)-Université Montpellier 1 (UM1)-Université Montpellier 2 - Sciences et Techniques (UM2)-Institut de Chimie du CNRS (INC), Laboratoire des Agrégats Moléculaires et Matériaux Inorganiques (LAMMI), Centre National de la Recherche Scientifique (CNRS)-Université Montpellier 2 - Sciences et Techniques (UM2), Materials Department, University of California [Santa Barbara] (UCSB), and University of California-University of California
Subjects: Battery (electricity), Intercalation (chemistry), Inorganic chemistry, Solid-state, 02 engineering and technology, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Ion, chemistry.chemical_compound, Mössbauer spectroscopy, Materials Chemistry, Electrochemistry, Organic chemistry, ComputingMilieux_MISCELLANEOUS, Renewable Energy, Sustainability and the Environment, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, Condensed Matter Physics, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, chemistry, Scientific method, Electrode, Ionic liquid, 0210 nano-technology
Abstract: Ionothermal synthesis has recently been used to prepare a fluorosulfate (LiFeSO 4 F) capable of reversibly intercalating Li at 3.6 V vs Li, making this material a serious contender to LiFePO 4 for HEV and electric vehicle applications. Although fluorosulfates are made from low cost and abundant starting materials, their synthesis is costly because of the use of ionic liquids as synthetic medium. Herein, we report a solid-state process by which LiFeSO 4 F can be synthesized without the use of ionic liquids but at the expense of both longer reaction time and weakly contaminated samples. Additionally, we show how powerful Mossbauer spectroscopy can be in the optimization of the various stages of electrode preparation as shown through the synthesis of LiFeSO 4 F and its implementation into an electrode. The importance of having Fe 3+ -free hydrated precursors to routinely obtain pure LiFeSO 4 F samples is shown together with the need to optimize ballmilling conditions to preserve Fe 3+ -free LiFeSO 4 F composites. Samples prepared via this low temperature solid-state process show battery performances approaching those of samples prepared using ionic liquids as synthetic medium. Furthermore, this process can be extended to the synthesis of the other members of the fluorosulfates AMSO 4 F family with A = Li, Na and M = Fe, Co, and Ni.
Published: 2010

32. Catalytic coatings on stainless steel prepared by sol–gel route

Author: Dimitri Truyen, Matthieu Courty, Pierre Alphonse, Florence Ansart, 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), Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), and Centre National de la Recherche Scientifique - CNRS (FRANCE)
Subjects: Catalytic film, Boehmite, Materials science, Matériaux, Alumina, Nanoparticle, 02 engineering and technology, Sol–gel, 010402 general chemistry, Peptization, 01 natural sciences, Catalysis, chemistry.chemical_compound, Specific surface area, Materials Chemistry, Thermal stability, Thixotropy, Sol-gel, Metallurgy, Metals and Alloys, Surfaces and Interfaces, [CHIM.MATE]Chemical Sciences/Material chemistry, 021001 nanoscience & nanotechnology, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Chemical engineering, chemistry, Alkoxide, 0210 nano-technology
Abstract: International audience; Stainless steel (flat and microstructured) substrates have been coated with sol–gel catalysts made up of metal nanoparticles (Rh, Ni, Pt) dispersed on alumina and alumina–ceria supports. The aluminum monohydroxyde (boehmite) sols were synthesized by hot hydrolysis/peptization of an aluminum alkoxide (Yoldas method). It is shown that the rheological properties of the sol, especially the thixotropy, play a key role on the homogeneity and the quality of the film deposited on the metal substrate. The catalyst layers have a very good adhesion, a thickness which can be easily controlled (in the range 0.1 to 10 μm), a large specific surface area and a good mechanical and thermal stability.
Published: 2006

33. Platinum/ceria/alumina catalysts on microstructures for carbon monoxide conversion

Author: Yves Schuurman, Pierre Alphonse, Matthieu Courty, Claudine Mirodatos, G. Germani, Institut National Polytechnique de Toulouse - INPT (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Centre National de la Recherche Scientifique - CNRS (FRANCE), IRCELYON, ProductionsScientifiques, Institut de recherches sur la catalyse et l'environnement de Lyon (IRCELYON), Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-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), Institut de recherches sur la catalyse (IRC), Centre National de la Recherche Scientifique (CNRS), and Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE)
Subjects: Materials science, Hydrogen purification, Matériaux, Inorganic chemistry, Proton exchange membrane fuel cell, chemistry.chemical_element, 02 engineering and technology, Activation energy, 010402 general chemistry, 7. Clean energy, 01 natural sciences, Hydrogen purifier, Catalysis, Water-gas shift reaction, Adsorption, Water-gas shift, Catalyst coating, Water gas, [CHIM.CATA] Chemical Sciences/Catalysis, Microreactors -Kinetics, General Chemistry, [CHIM.CATA]Chemical Sciences/Catalysis, 021001 nanoscience & nanotechnology, 0104 chemical sciences, sol–gel, chemistry, 0210 nano-technology, Platinum
Abstract: International audience; Platinum/ceria/alumina catalysts have been prepared by a sol–gel method and coated in the microchannels of stainless steel platelets. These catalysts are very active for the water-gas shift reaction between 300 and 400°C. Moreover, they are non-pyrophoric and thus well suited for the purification of hydrogen for PEM fuel cells. The obtained coatings show good adherence and catalytic activity. The influence of the amount of platinum and ceria as well as the effect of a binder on the catalytic performance has been investigated. The samples have been characterized before reaction by XRD, SEM and by N2 adsorption measurements. The kinetics, free from internal diffusion limitations, over these thin films have been described by a power law rate equation. An activation energy of 86 kJ/mol has been found and at 260 °C the TOF corresponds to 0.6 ± 0.1 s−1 for all investigated samples. The superior activity of the platelets compared to the powder samples is attributed to the diffusion limitations inside the powder pellets. Thus catalysts deposited on microstructured platelets lead to a better platinum utilization.
Published: 2005

34. Surface and porosity of nanocrystalline boehmite xerogels

Author: Pierre Alphonse, Matthieu Courty, Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Centre National de la Recherche Scientifique - CNRS (FRANCE), 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), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)
Subjects: Boehmite, Materials science, Surface Properties, Matériaux, Mineralogy, Specific surface area, Aluminum Hydroxide, 02 engineering and technology, 010402 general chemistry, Peptization, 01 natural sciences, Nitric Acid, Sensitivity and Specificity, law.invention, [SPI.MAT]Engineering Sciences [physics]/Materials, Biomaterials, Colloid and Surface Chemistry, Microscopy, Electron, Transmission, X-Ray Diffraction, law, Aluminum Oxide, Crystallization, Particle Size, Porosity, PSD, Hydrolysis, Temperature, 021001 nanoscience & nanotechnology, Nanocrystalline material, 0104 chemical sciences, Surfaces, Coatings and Films, Electronic, Optical and Magnetic Materials, Nanostructures, Chemical engineering, Comparative plot, Crystallite, Particle size, 0210 nano-technology, Gels
Abstract: Boehmite xerogels are prepared by hydrolysis of Al(OC4H9)3 followed by peptization with HNO3 (H+/Al = 0, 0.07, 0.2). XRD and TEM show that these gels are made of nanosized crystals (5-9 nm in width and 3 nm thick). According to the amount of acid, no significant differences are found in size and shape, but only in the spatial arrangement of the crystallites. Nitrogen adsorption-desorption isotherms of nonpeptized gels are of type IV, whereas isotherms of peptized gels are of type I. These isotherms are analyzed by the t-plot method. The majority of pore volume results from intercrystalline mesopores, but the peptized gels also contain intercrystalline micropores. The particle packing is very dense for the gel peptized with H+/Al = 0.2 (porosity = 0.26), but it is less dense in non-peptized gel (porosity = 0.44). Heating these gels under vacuum creates, from 250 degrees C onwards, an intracrystalline microporosity resulting from the conversion of boehmite into transition alumina. But heating also causes intercrystalline micropores collapsing. The specific surface area increases up to a limit temperature (300 degrees C for nonpeptized gels and 400 degrees C for peptized) beyond which sintering of the particles begins and the surface decreases. The PSD are calculated assuming a cylindrical pore geometry and using the corrected Kelvin equation proposed by Kruk et al. Peptized xerogels give a monomodal distribution with a maximum near 2 nm and no pores are larger than 6 nm. Nonpeptized gels have a bimodal distribution with a narrow peak near to 2 nm and a broad unsymmetrical peak with a maximum at 4 nm. Heating in air above 400 degrees C has a strong effect on the porosity. As the temperature increases, there is a broadening of the distribution and a marked decrease of small pores (below 3 nm). However, even after treatment at 800 degrees C, micropores are still present.
Published: 2005

35. Structure and thermal behavior of nanocrystalline boehmite

Author: Pierre Alphonse, Matthieu Courty, Institut National Polytechnique de Toulouse - Toulouse INP (FRANCE), Université Toulouse III - Paul Sabatier - UT3 (FRANCE), Centre National de la Recherche Scientifique - CNRS (FRANCE), 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), and Université Fédérale Toulouse Midi-Pyrénées-Institut de Chimie du CNRS (INC)
Subjects: Boehmite, Materials science, Matériaux, chemistry.chemical_element, Mineralogy, 02 engineering and technology, Activation energy, 010402 general chemistry, Peptization, 01 natural sciences, Transition alumina, Aluminium, Specific surface area, medicine, Dehydration, Physical and Theoretical Chemistry, Instrumentation, [CHIM.MATE]Chemical Sciences/Material chemistry, Computer simulation, 021001 nanoscience & nanotechnology, Condensed Matter Physics, medicine.disease, Nanocrystalline material, 0104 chemical sciences, chemistry, Chemical engineering, Non-isothermal kinetics, Particle, 0210 nano-technology
Abstract: International audience; First, the structural features of nanocrystalline boehmite synthesized by hydrolysis of aluminum sec-butoxide according to the Yoldas method are reported. The nanosized boehmite consists of rectangular platelets averaging 8 by 9 nm and 2–3 nm in thickness which contain a large excess of water. Dehydration by heating under vacuum induced an increase in the specific surface area, down to a minimum water content ( 0.2 H2O per Al2O3); values up to 470 m2/g can be reached. However this enlargement of specific surface area only results from water loss, the surface area remaining constant. The particle morphology, the excess of water, as well as the specific surface area, depend on the amount of acid used for the peptization during the synthesis. Second, a comprehensive investigation of the dehydration kinetics is presented. The simulations of the non-isothermal experiments at constant heating rates show that thermally stimulated transformation of nanocrystalline boehmite into alumina can be accurately modeled by a 4-reaction mechanism involving: (I) the loss of physisorbed water, (II) the loss of chemisorbed water, (III) the conversion of boehmite into transition alumina, (IV) the dehydration of transition alumina (loss of residual hydroxyl groups). The activation energy of each step is found to be very similar for experiments done in various conditions (heating rate, atmosphere, kind of sample,...).
Published: 2005

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35 results on '"Matthieu, Courty"'

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

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

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

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

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

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

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

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

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

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

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

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

13. 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

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

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

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

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

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

19. An Oxysulfate Fe2O(SO4)2 Electrode for Sustainable Li-Based Batteries

20. Biomass derived ionic liquids: synthesis from natural organic acids, characterization, toxicity, biodegradation and use as solvents for catalytic hydrogenation processes

21. A new sensitive organic/inorganic hybrid material based on titanium oxide for the potentiometric detection of iron(III)

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

23. Ionothermal Synthesis of Tailor-Made LiFePO4 Powders for Li-Ion Battery Applications

24. Tetrabutylammonium prolinate-based ionic liquids:A combined asymmetric catalysis, antimicrobial toxicity and biodegradation assessment

25. Click Reactions as a Key Step for an Efficient and Selective Synthesis of D-Xylose-Based ILs

26. Preparation and characterization of LiNi0.5Mn1.5O4−δ thin films taking advantage of correlations with powder samples behavior

27. Syntheses and characterisation of hydrophobic ionic liquids containing trialkyl(2-ethoxy-2-oxoethyl)ammonium or N-(1-methylpyrrolidyl-2-ethoxy-2-oxoethyl)ammonium cations

28. A green Li-organic battery working as a fuel cell in case of emergency

29. Calix[4]arene-modified silica nanoparticles for the potentiometric detection of iron (III) in aqueous solution

30. Single-ion polymer electrolytes based on a delocalized polyanion for lithium batteries

31. Fluorosulfate Positive Electrodes for Li-Ion Batteries Made via a Solid-State Dry Process

32. Catalytic coatings on stainless steel prepared by sol–gel route

33. Platinum/ceria/alumina catalysts on microstructures for carbon monoxide conversion

34. Surface and porosity of nanocrystalline boehmite xerogels

35. Structure and thermal behavior of nanocrystalline boehmite

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35 results on '"Matthieu, Courty"'

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