Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Comparison of Anion Reorientational Dynamics in MCB 9 H 10 and M 2 B 10 H 10 (M = Li, Na) via Nuclear Magnetic Resonance and Quasielastic Neutron Scattering Studies

Abstract

The disordered phases of the 1-carba-closo-decaborates LiCB9H10 and NaCB9H10 exhibit the best solid-state ionic conductivities to date among all known polycrystalline competitors, likely facilitated in part by the highly orientationally mobile CB9H10- anions. We have undertaken both NMR and quasielastic neutron scattering (QENS) measurements to help characterize the monovalent anion reorientational mobilities and mechanisms associated with these two compounds and to compare their anion reorientational behaviors with those for the divalent B10H102- anions in the related Li2B10H10 and Na2B10H10 compounds. NMR data show that the transition from the low-T ordered to the high-T disordered phase for both LiCB9H10 and NaCB9H10 is accompanied by a nearly two-orders-of-magnitude increase in the reorientational jump rate of CB9H10- anions. QENS measurements of the various disordered compounds indicate anion jump correlation frequencies on the order of 1010-1011 s-1 and confirm that NaCB9H10 displays jump frequencies about 60% to 120% higher than those for LiCB9H10 and Na2B10H10 at comparable temperatures. The Q-dependent quasielastic scattering suggests similar small-angular-jump reorientational mechanisms for the different disordered anions, changing from more uniaxial in character at lower temperatures to more multidimensional at higher temperatures, although still falling short of full three-dimensional rotational diffusion below 500 K within the nanosecond neutron window.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [1];  [1];  [1];  [3];  [4];  [5];  [6]
+ Show Author Affiliations
  1. Russian Academy of Sciences (RAS), Ekaterinburg (Russian Federation). Inst. of Metal Physics
  2. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research; National Renewable Energy Lab. (NREL), Golden, CO (United States)
  3. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research; Univ. of Maryland, College Park, MD (United States). Dept. of Materials Science and Engineering
  4. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  5. Tohoku Univ., Sendai (Japan). Inst. for Materials Research; Tohoku Univ., Sendai (Japan). WPI-Advanced Inst. for Materials Research
  6. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States). Center for Neutron Research
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office; USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); Russian Foundation for Basic Research; Japan Society for the Promotion of Science (JSPS)
OSTI Identifier:
1345720
Report Number(s):
NREL/JA-5900-68058
Journal ID: ISSN 1932-7447
Grant/Contract Number:  
AC36-08GO28308; AC04-94AL85000; DMR-0944772; 15-9-2-9; DMR-1508249; 2682031; 25220911
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 2; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; NMR; quasielastic neutron scattering; anions

Citation Formats

Soloninin, Alexei V., Dimitrievska, Mirjana, Skoryunov, Roman V., Babanova, Olga A., Skripov, Alexander V., Tang, Wan Si, Stavila, Vitalie, Orimo, Shin-ichi, and Udovic, Terrence J. Comparison of Anion Reorientational Dynamics in MCB 9 H 10 and M 2 B 10 H 10 (M = Li, Na) via Nuclear Magnetic Resonance and Quasielastic Neutron Scattering Studies. United States: N. p., 2016. Web. doi:10.1021/acs.jpcc.6b09113.
Copy to clipboard
Soloninin, Alexei V., Dimitrievska, Mirjana, Skoryunov, Roman V., Babanova, Olga A., Skripov, Alexander V., Tang, Wan Si, Stavila, Vitalie, Orimo, Shin-ichi, & Udovic, Terrence J. Comparison of Anion Reorientational Dynamics in MCB 9 H 10 and M 2 B 10 H 10 (M = Li, Na) via Nuclear Magnetic Resonance and Quasielastic Neutron Scattering Studies. United States. https://doi.org/10.1021/acs.jpcc.6b09113
Copy to clipboard
Soloninin, Alexei V., Dimitrievska, Mirjana, Skoryunov, Roman V., Babanova, Olga A., Skripov, Alexander V., Tang, Wan Si, Stavila, Vitalie, Orimo, Shin-ichi, and Udovic, Terrence J. Tue . "Comparison of Anion Reorientational Dynamics in MCB 9 H 10 and M 2 B 10 H 10 (M = Li, Na) via Nuclear Magnetic Resonance and Quasielastic Neutron Scattering Studies". United States. https://doi.org/10.1021/acs.jpcc.6b09113. https://www.osti.gov/servlets/purl/1345720.
Copy to clipboard
@article{osti_1345720,
title = {Comparison of Anion Reorientational Dynamics in MCB 9 H 10 and M 2 B 10 H 10 (M = Li, Na) via Nuclear Magnetic Resonance and Quasielastic Neutron Scattering Studies},
author = {Soloninin, Alexei V. and Dimitrievska, Mirjana and Skoryunov, Roman V. and Babanova, Olga A. and Skripov, Alexander V. and Tang, Wan Si and Stavila, Vitalie and Orimo, Shin-ichi and Udovic, Terrence J.},
abstractNote = {The disordered phases of the 1-carba-closo-decaborates LiCB9H10 and NaCB9H10 exhibit the best solid-state ionic conductivities to date among all known polycrystalline competitors, likely facilitated in part by the highly orientationally mobile CB9H10- anions. We have undertaken both NMR and quasielastic neutron scattering (QENS) measurements to help characterize the monovalent anion reorientational mobilities and mechanisms associated with these two compounds and to compare their anion reorientational behaviors with those for the divalent B10H102- anions in the related Li2B10H10 and Na2B10H10 compounds. NMR data show that the transition from the low-T ordered to the high-T disordered phase for both LiCB9H10 and NaCB9H10 is accompanied by a nearly two-orders-of-magnitude increase in the reorientational jump rate of CB9H10- anions. QENS measurements of the various disordered compounds indicate anion jump correlation frequencies on the order of 1010-1011 s-1 and confirm that NaCB9H10 displays jump frequencies about 60% to 120% higher than those for LiCB9H10 and Na2B10H10 at comparable temperatures. The Q-dependent quasielastic scattering suggests similar small-angular-jump reorientational mechanisms for the different disordered anions, changing from more uniaxial in character at lower temperatures to more multidimensional at higher temperatures, although still falling short of full three-dimensional rotational diffusion below 500 K within the nanosecond neutron window.},
doi = {10.1021/acs.jpcc.6b09113},
journal = {Journal of Physical Chemistry. C},
number = 2,
volume = 121,
place = {United States},
year = {Tue Dec 13 00:00:00 EST 2016},
month = {Tue Dec 13 00:00:00 EST 2016}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acs.jpcc.6b09113
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 30 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Exceptional Superionic Conductivity in Disordered Sodium Decahydro- closo -decaborate
journal, October 2014

  • Udovic, Terrence J.; Matsuo, Motoaki; Tang, Wan Si
  • Advanced Materials, Vol. 26, Issue 45
  • DOI: 10.1002/adma.201403157

Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions
journal, January 2015

  • Tang, Wan Si; Unemoto, Atsushi; Zhou, Wei
  • Energy & Environmental Science, Vol. 8, Issue 12
  • DOI: 10.1039/C5EE02941D

Liquid‐Like Ionic Conduction in Solid Lithium and Sodium Monocarba‐ closo ‐Decaborates Near or at Room Temperature
journal, February 2016

  • Tang, Wan Si; Matsuo, Motoaki; Wu, Hui
  • Advanced Energy Materials, Vol. 6, Issue 8
  • DOI: 10.1002/aenm.201502237

Complex high-temperature phase transitions in Li2B12H12 and Na2B12H12
journal, April 2014

The structure of monoclinic Na 2 B 10 H 10 : a combined diffraction, spectroscopy, and theoretical approach
journal, January 2015

  • Wu, Hui; Tang, Wan Si; Zhou, Wei
  • CrystEngComm, Vol. 17, Issue 18
  • DOI: 10.1039/C5CE00369E

Nuclear Magnetic Resonance Study of Atomic Motion in A 2 B 12 H 12 (A = Na, K, Rb, Cs): Anion Reorientations and Na + Mobility
journal, November 2013

  • Skripov, Alexander V.; Babanova, Olga A.; Soloninin, Alexei V.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 49
  • DOI: 10.1021/jp4106585

Anion Reorientations in the Superionic Conducting Phase of Na 2 B 12 H 12
journal, July 2014

  • Verdal, Nina; Udovic, Terrence J.; Stavila, Vitalie
  • The Journal of Physical Chemistry C, Vol. 118, Issue 31
  • DOI: 10.1021/jp506252c

Structural Behavior of Li 2 B 10 H 10
journal, March 2015

  • Wu, Hui; Tang, Wan Si; Stavila, Vitalie
  • The Journal of Physical Chemistry C, Vol. 119, Issue 12
  • DOI: 10.1021/acs.jpcc.5b00533

Anion Reorientations and Cation Diffusion in LiCB 11 H 12 and NaCB 11 H 12 : 1 H, 7 Li, and 23 Na NMR Studies
journal, November 2015

  • Skripov, Alexander V.; Skoryunov, Roman V.; Soloninin, Alexei V.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 48
  • DOI: 10.1021/acs.jpcc.5b10055

Dynamical Structure, Bonding, and Thermodynamics of the Superionic Sublattice in α − AgI
journal, October 2006

X-ray Crystal Structure Analysis of Sodium-Ion Conductivity in 94 Na 3 PS 4 ⋅6 Na 4 SiS 4 Glass-Ceramic Electrolytes
journal, June 2014

  • Tanibata, Naoto; Noi, Kousuke; Hayashi, Akitoshi
  • ChemElectroChem, Vol. 1, Issue 7
  • DOI: 10.1002/celc.201402016

Structural and Mechanistic Insights into Fast Lithium-Ion Conduction in Li 4 SiO 4 –Li 3 PO 4 Solid Electrolytes
journal, July 2015

  • Deng, Yue; Eames, Christopher; Chotard, Jean-Noël
  • Journal of the American Chemical Society, Vol. 137, Issue 28
  • DOI: 10.1021/jacs.5b04444

Stabilizing lithium and sodium fast-ion conduction in solid polyhedral-borate salts at device-relevant temperatures
journal, July 2016

Stabilizing Superionic-Conducting Structures via Mixed-Anion Solid Solutions of Monocarba- closo -borate Salts
journal, September 2016

Hydrogen Diffusion in Laves-Phase Compounds
journal, December 2003

The Disk Chopper Spectrometer at NIST: a new instrument for quasielastic neutron scattering studies
journal, August 2003

DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data
journal, November 2009

  • Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming
  • Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6
  • DOI: 10.6028/jres.114.025

Structural and Dynamical Properties of NaBH 4 and KBH 4 : NMR and Synchrotron X-ray Diffraction Studies
journal, February 2010

  • Babanova, Olga A.; Soloninin, Alexei V.; Stepanov, Adolf P.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 8
  • DOI: 10.1021/jp9119606

The low-temperature structural behavior of sodium 1-carba-closo-decaborate: NaCB9H10
journal, November 2016

Hydrogen diffusion in the metallic glass a - Zr 3 RhH 3.5
journal, April 1988

Low-temperature localized motion of hydrogen and electronic structure transition in hexagonal-close-packed scandium
journal, February 1989

Nuclear Magnetic Resonance Study of Reorientational Motion in α-Mg(BH 4 ) 2
journal, June 2010

  • Skripov, Alexander V.; Soloninin, Alexei V.; Babanova, Olga A.
  • The Journal of Physical Chemistry C, Vol. 114, Issue 28
  • DOI: 10.1021/jp1037206

Nuclear magnetic resonance studies of atomic motion in borohydride-based materials: Fast anion reorientations and cation diffusion
journal, October 2015

NMR Study of Molecular Dynamics in Complex Metal Borohydride LiZn 2 (BH 4 ) 5
journal, October 2013

  • Gradišek, Anton; Ravnsbæk, Dorthe B.; Vrtnik, Stanislav
  • The Journal of Physical Chemistry C, Vol. 117, Issue 41
  • DOI: 10.1021/jp407620r

Nuclear Magnetic Resonance Studies of Reorientational Motion and Li Diffusion in LiBH 4 –LiI Solid Solutions
journal, December 2012

  • Skripov, Alexander V.; Soloninin, Alexei V.; Rude, Line H.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 50
  • DOI: 10.1021/jp3080892

Evolution of the Reorientational Motions of the Tetrahydroborate Anions in Hexagonal LiBH 4 –LiI Solid Solution by High- Q Quasielastic Neutron Scattering
journal, May 2013

  • Verdal, Nina; Udovic, Terrence J.; Rush, John J.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 23
  • DOI: 10.1021/jp403636k

Diffusion in periodic potentials
journal, June 1977

  • Dieterich, W.; Peschel, I.; Schneider, W. R.
  • Zeitschrift f�r Physik B Condensed Matter and Quanta, Vol. 27, Issue 2
  • DOI: 10.1007/BF01313607

Dynamics of Pyramidal SiH 3 – Ions in ASiH 3 (A = K and Rb) Investigated with Quasielastic Neutron Scattering
journal, March 2016

  • Österberg, Carin; Fahlquist, Henrik; Häussermann, Ulrich
  • The Journal of Physical Chemistry C, Vol. 120, Issue 12
  • DOI: 10.1021/acs.jpcc.6b00363

Structural and Dynamical Trends in Alkali-Metal Silanides Characterized by Neutron-Scattering Methods
journal, September 2016

  • Tang, Wan Si; Dimitrievska, Mirjana; Chotard, Jean-Noël
  • The Journal of Physical Chemistry C, Vol. 120, Issue 38
  • DOI: 10.1021/acs.jpcc.6b06591

Effects of partial halide anion substitution on reorientational motion in NaBH4: A nuclear magnetic resonance study
journal, July 2015

Second moment expressions for solids containing reorienting nuclear spins
journal, February 1973

  • Dereppe, J. M.
  • The Journal of Chemical Physics, Vol. 58, Issue 3
  • DOI: 10.1063/1.1679316

Crystal structures of M 2 [B 10 H 10 ] (M = Na, K, Rb) via real-space simulated annealing powder techniques
journal, March 2005

  • Hofmann, K.; Albert, Barbara
  • Zeitschrift für Kristallographie - Crystalline Materials, Vol. 220, Issue 2-3
  • DOI: 10.1524/zkri.220.2.142.59144
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    First-Principles Investigation of the Mechanical and Thermodynamic Properties of the Metal-Borohydrides as Electrolytes for Solid-State Batteries
    journal, January 2019

    • Chen, Haichuan; Hong, Tao
    • Journal of The Electrochemical Society, Vol. 166, Issue 4
    • DOI: 10.1149/2.0071904jes

    Carbon Incorporation and Anion Dynamics as Synergistic Drivers for Ultrafast Diffusion in Superionic LiCB 11 H 12 and NaCB 11 H 12
    journal, February 2018

    • Dimitrievska, Mirjana; Shea, Patrick; Kweon, Kyoung E.
    • Advanced Energy Materials, Vol. 8, Issue 15
    • DOI: 10.1002/aenm.201703422
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: