Crystal Structures, Local Atomic Environments, and Ion Diffusion Mechanisms of Scandium-Substituted Sodium Superionic Conductor (NASICON) Solid Electrolytes

Autor: Deng, Y, Eames, C, Nguyen, LHB, Pecher, O, Griffith, KJ, Courty, M, Fleutot, B, Chotard, JN, Grey, CP, Islam, MS, Masquelier, C
Přispěvatelé: Department of chemistry, University of Bath [Bath], 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)-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), University of Cambridge [UK] (CAM), Advanced Lithium Energy Storage Systems - ALISTORE-ERI (ALISTORE-ERI), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS), Eames, C [0000-0002-5548-2655], Griffith, KJ [0000-0002-8096-906X], Chotard, JN [0000-0002-9867-7954], Grey, CP [0000-0001-5572-192X], Islam, MS [0000-0003-3882-0285], Masquelier, C [0000-0001-7289-1015], Apollo - University of Cambridge Repository
Jazyk: angličtina
Rok vydání: 2018
Předmět:
Zdroj: Chemistry of Materials
Chemistry of Materials, 2018, 30 (8), pp.2618-2630. ⟨10.1021/acs.chemmater.7b05237⟩
'Chemistry of Materials ', vol: 30, pages: 2618-2630 (2018)
ISSN: 0897-4756
1520-5002
DOI: 10.1021/acs.chemmater.7b05237⟩
Popis: International audience; The importance of exploring new solid electro-lytes for all-solid-state batteries has led to significant interest in NASICON-type materials. Here, the Sc3+-substituted NASICON compositions (NaScZr2-x)-Sc-3-Zr-x(SiO4)(2-x)(PO4)(1+x) (termed N3) and Na2ScyZr2-y(SiO4)(1-y)(PO4)(2+y) (termed N2) (x, y = 0-1) are studied as model Na+-ion conducting electrolytes for solid-state batteries. The influence of Sc3+ substitution on the crystal structures and local atomic environments has been characterized by powder X-ray diffraction (XRD) and neutron powder diffraction (NPD), as well as solid-state Na-23, P-31, and Si-29 nuclear magnetic resonance (NMR) spectroscopy. A phase transition between 295 and 473 K from monoclinic C2/c to rhombohedral R (3) over barc is observed for the N3 compositions, while N2 compositions crystallize in a rhombohedral R (3) over barc unit cell in this temperature range. Alternating current (AC) impedance spectroscopy, molecular dynamics (MD), and high temperature Na-23 NMR studies are in good agreement, showing that, with a higher Sc3+ concentration, the ionic conductivity (of about 10(-4) S/cm at 473 K) decreases and the activation energy for ion diffusion increases. Na-23 NMR experiments indicate that the nature of the Na+-ion motion is two-dimensional on the local atomic scale of NMR although the long-range diffusion pathways are three-dimensional. In addition, a combination of MD, bond valence, maximum entropy/Rietveld, and van Hove correlation methods has been used to reveal that the Na+-ion diffusion in these NASICON materials is three-dimensional and that there is a continuous exchange of sodium ions between Na(1) and Na(2) sites.
Databáze: OpenAIRE
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