skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

The importance of exploring new solid electrolytes for all-solid-state batteries has led to significant interest in NASICON-type materials. In this work, the Sc3+-substituted NASICON compositions Na3ScxZr2–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 23Na, 31P, and 29Si nuclear magnetic resonance (NMR) spectroscopy. A phase transition between 295 and 473 K from monoclinic C2/c to rhombohedral $$R\bar{3}c$$ is observed for the N3 compositions, while N2 compositions crystallize in a rhombohedral $$R\bar{3}c$$ unit cell in this temperature range. Alternating current (AC) impedance spectroscopy, molecular dynamics (MD), and high temperature 23Na 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. 23Na 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,more » 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.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [3]; ORCiD logo [3];  [4];  [5]; ORCiD logo [6]; ORCiD logo [7]; ORCiD logo [8]; ORCiD logo [5]
  1. Univ. Picardie Jules Verne, Cedex Amiens (France); Univ. of Bath (United Kingdom); Réseau sur le Stockage Électrochimique de l’Énergie (RS2E), Amiens (France); ALISTORE European Research Inst., Cedex Amiens (France)
  2. Univ. of Bath (United Kingdom)
  3. Univ. of Cambridge (United Kingdom)
  4. Univ. Picardie Jules Verne, Cedex Amiens (France)
  5. Univ. Picardie Jules Verne, Cedex Amiens (France); Réseau sur le Stockage Électrochimique de l’Énergie (RS2E), Amiens (France); ALISTORE European Research Inst., Cedex Amiens (France)
  6. Univ. Picardie Jules Verne, Cedex Amiens (France); Réseau sur le Stockage Électrochimique de l’Énergie (RS2E), Amiens (France)
  7. Univ. of Cambridge (United Kingdom); ALISTORE European Research Inst., Cedex Amiens (France)
  8. Univ. of Bath (United Kingdom); ALISTORE European Research Inst., Cedex Amiens (France)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
ALISTORE ERI; CNRS; ERASMUS Mundus; Winston Churchill Foundation; Herchel Smith Scholarship; Engineering and Physical Sciences Research Council (EPSRC); Higher Education Funding Council for England (HEFCE); Science and Technology Facilities Council (STFC)
OSTI Identifier:
1436784
Grant/Contract Number:  
EP/K016288/1; EP/L000202/1
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 30; Journal Issue: 8; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Diffusion; Crystal structure; Ions; Physical and chemical processes; Ionic conductivity

Citation Formats

Deng, Yue, Eames, Christopher, Nguyen, Long H. B., Pecher, Oliver, Griffith, Kent J., Courty, Matthieu, Fleutot, Benoit, Chotard, Jean-Noël, Grey, Clare P., Islam, M. Saiful, and Masquelier, Christian. Crystal Structures, Local Atomic Environments, and Ion Diffusion Mechanisms of Scandium-Substituted Sodium Superionic Conductor (NASICON) Solid Electrolytes. United States: N. p., 2018. Web. doi:10.1021/acs.chemmater.7b05237.
Deng, Yue, Eames, Christopher, Nguyen, Long H. B., Pecher, Oliver, Griffith, Kent J., Courty, Matthieu, Fleutot, Benoit, Chotard, Jean-Noël, Grey, Clare P., Islam, M. Saiful, & Masquelier, Christian. Crystal Structures, Local Atomic Environments, and Ion Diffusion Mechanisms of Scandium-Substituted Sodium Superionic Conductor (NASICON) Solid Electrolytes. United States. https://doi.org/10.1021/acs.chemmater.7b05237
Deng, Yue, Eames, Christopher, Nguyen, Long H. B., Pecher, Oliver, Griffith, Kent J., Courty, Matthieu, Fleutot, Benoit, Chotard, Jean-Noël, Grey, Clare P., Islam, M. Saiful, and Masquelier, Christian. 2018. "Crystal Structures, Local Atomic Environments, and Ion Diffusion Mechanisms of Scandium-Substituted Sodium Superionic Conductor (NASICON) Solid Electrolytes". United States. https://doi.org/10.1021/acs.chemmater.7b05237. https://www.osti.gov/servlets/purl/1436784.
@article{osti_1436784,
title = {Crystal Structures, Local Atomic Environments, and Ion Diffusion Mechanisms of Scandium-Substituted Sodium Superionic Conductor (NASICON) Solid Electrolytes},
author = {Deng, Yue and Eames, Christopher and Nguyen, Long H. B. and Pecher, Oliver and Griffith, Kent J. and Courty, Matthieu and Fleutot, Benoit and Chotard, Jean-Noël and Grey, Clare P. and Islam, M. Saiful and Masquelier, Christian},
abstractNote = {The importance of exploring new solid electrolytes for all-solid-state batteries has led to significant interest in NASICON-type materials. In this work, the Sc3+-substituted NASICON compositions Na3ScxZr2–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 23Na, 31P, and 29Si nuclear magnetic resonance (NMR) spectroscopy. A phase transition between 295 and 473 K from monoclinic C2/c to rhombohedral $R\bar{3}c$ is observed for the N3 compositions, while N2 compositions crystallize in a rhombohedral $R\bar{3}c$ unit cell in this temperature range. Alternating current (AC) impedance spectroscopy, molecular dynamics (MD), and high temperature 23Na 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. 23Na 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.},
doi = {10.1021/acs.chemmater.7b05237},
url = {https://www.osti.gov/biblio/1436784}, journal = {Chemistry of Materials},
issn = {0897-4756},
number = 8,
volume = 30,
place = {United States},
year = {2018},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 35 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Building better batteries
journal, February 2008


Towards greener and more sustainable batteries for electrical energy storage
journal, November 2014


Towards high energy density sodium ion batteries through electrolyte optimization
journal, January 2013


The Emerging Chemistry of Sodium Ion Batteries for Electrochemical Energy Storage
journal, February 2015


Solid Electrolyte: the Key for High-Voltage Lithium Batteries
journal, October 2014


Design principles for solid-state lithium superionic conductors
journal, August 2015


Fast Na+-ion transport in skeleton structures
journal, February 1976


NASICON type materials - Na3M2(PO4)3 (M=Sc, Cr, Fe): Na+-Na+ correlations and phase transitions
journal, December 1983


Discovery of a Sodium-Ordered Form of Na 3 V 2 (PO 4 ) 3 below Ambient Temperature
journal, August 2015


Na-ion diffusion in a NASICON-type solid electrolyte: a density functional study
journal, January 2016


A hybrid solid electrolyte for flexible solid-state sodium batteries
journal, January 2015


Crystal structure and ionic conductivity in Na4Zr2Si3O12
journal, September 1981


Disorder of tetrahedra in Nasicon-type structure—I.
journal, January 1986


Stoichiometry and phase transitions in NASICON type compounds
journal, December 1983


Fast ion transport in the NASICON analog Na3Sc2(PO4)3: Structure and conductivity
journal, December 1983


Ionic conductivity of the Na1+xM x III Zr2?x(PO4)3 systems (M = Al, Ga, Cr, Fe, Sc, In, Y, Yb)
journal, September 1990


Fast Na + Ion Conduction in NASICON-Type Na 3.4 Sc 2 (SiO 4 ) 0.4 (PO 4 ) 2.6 Observed by 23 Na NMR Relaxometry
journal, January 2017


Recent advances in magnetic structure determination by neutron powder diffraction
journal, October 1993


31P NMR Study of Powder and Single-Crystal Samples of Ammonium Dihydrogen Phosphate: Effect of Homonuclear Dipolar Coupling
journal, March 1994


Generalized Gradient Approximation Made Simple
journal, October 1996


Special points for Brillouin-zone integrations
journal, June 1976


Modeling Ti/Ge Distribution in LiTi 2– x Ge x (PO 4 ) 3 NASICON Series by 31 P MAS NMR and First-Principles DFT Calculations
journal, July 2016


Influence of Si/P ordering on Na+ transport in NASICONs
journal, January 2013


Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Role of Na + Interstitials and Dopants in Enhancing the Na + Conductivity of the Cubic Na 3 PS 4 Superionic Conductor
journal, December 2015


Crystal structure of the solid electrolyte Na3Sc2(PO4)3 in the temperature range 27?350�C
journal, January 1984


Materials’ Methods: NMR in Battery Research
journal, November 2016


29Si and 31P MAS NMR study of the NASICON system Na1+χZr2(SiO4)χ(PO4)3-χ
journal, May 1988


Structure, phase separation and Li dynamics in sol–gel-derived Li1+xAlxGe2−x(PO4)3
journal, August 2015


Li 3 Mo 4 P 5 O 24 : A Two-Electron Cathode for Lithium-Ion Batteries with Three-Dimensional Diffusion Pathways
journal, March 2016


Works referencing / citing this record:

Systematic evaluation of lithium-excess polyanionic compounds as multi-electron reaction cathodes
journal, January 2019


A NASICON‐Type Positive Electrode for Na Batteries with High Energy Density: Na 4 MnV(PO 4 ) 3
journal, August 2018


Coexistence of three types of sodium motion in double molybdate Na 9 Sc(MoO 4 ) 6 : 23 Na and 45 Sc NMR data and ab initio calculations
journal, January 2020


Stabilization of a 4.5 V Cr 4+ /Cr 3+ redox reaction in NASICON-type Na 3 Cr 2 (PO 4 ) 3 by Ti substitution
journal, January 2019


New KRb 2 Sb 4 BO 13 and Rb 3 Sb 4 BO 13 compounds prepared by Rb + /K + ion exchange from the K 3 Sb 4 BO 13 ion conductor
journal, January 2019


Computational investigation of the Mg-ion conductivity and phase stability of MgZr 4 (PO 4 ) 6
journal, January 2019


Hybrid DFT investigation of the energetics of Mg ion diffusion in α-MoO 3
journal, January 2018