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Title: Carbon Incorporation and Anion Dynamics as Synergistic Drivers for Ultrafast Diffusion in Superionic LiCB 11H 12 and NaCB 11H 12

Abstract

The disordered phases ofLiCB 11H 12 and NaCB 11H 12 possess superb superionic conductivities that make them suitable as solid electrolytes. In these materials, cation diffusion correlates with high orientational mobilities of the CB 11H 12 - anions; however, the precise relationship has yet to be demonstrated. In this work, ab initio molecular dynamics and quasielastic neutron scattering are combined to probe anion reorientations and their mechanistic connection to cation mobility over a range of timescales and temperatures. It is found that anions do not rotate freely, but rather transition rapidly between orientations defined by the cation sublattice symmetry. The symmetry-breaking carbon atom in CB 11H 12 - also plays a critical role by perturbing the energy landscape along the instantaneous orientation of the anion dipole, which couples fluctuations in the cation probability density directly to the anion motion. Anion reorientation rates exceed 3 x 10 10 s -1, suggesting the underlying energy landscape fluctuates dynamically on diffusion-relevant timescales. Furthermore, carbon is found to modify the orientational preferences of the anions and aid rotational mobility, creating additional symmetry incompatibilities that inhibit ordering. The results suggest that synergy between the anion reorientational dynamics and the carbon-modified cation-anion interaction accounts for themore » higher ionic conductivity in CB 11H 12 - salts compared with B 12H 12 2-.« less

Authors:
 [1];  [2];  [2];  [3];  [2];  [1];  [4];  [5];  [6]; ORCiD logo [2]
  1. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Maryland, College Park, MD (United States)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  3. Univ. of Antwerp (Belgium)
  4. Ural Division of the Russian Academy of Sciences, Ekaterinburg (Russian Federation)
  5. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  6. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Hydrogen and Fuel Cell Technologies Program (EE-3F); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1425573
Alternate Identifier(s):
OSTI ID: 1422013; OSTI ID: 1542730
Report Number(s):
NREL/JA-5900-71080; LLNL-JRNL-740042
Journal ID: ISSN 1614-6832; TRN: US1802123
Grant/Contract Number:  
AC36-08GO28308; AC52-07NA27344; AC04-94AL85000; 15-ERD-022
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 8; Journal Issue: 8; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ab initio molecular dynamics; closo-borates; quasielastic neutron scattering; solid electrolytes; superionic

Citation Formats

Dimitrievska, Mirjana, Shea, Patrick, Kweon, Kyoung E., Bercx, Marnik, Varley, Joel B., Tang, Wan Si, Skripov, Alexander V., Stavila, Vitalie, Udovic, Terrence J., and Wood, Brandon C. Carbon Incorporation and Anion Dynamics as Synergistic Drivers for Ultrafast Diffusion in Superionic LiCB11H12 and NaCB11H12. United States: N. p., 2018. Web. doi:10.1002/aenm.201703422.
Dimitrievska, Mirjana, Shea, Patrick, Kweon, Kyoung E., Bercx, Marnik, Varley, Joel B., Tang, Wan Si, Skripov, Alexander V., Stavila, Vitalie, Udovic, Terrence J., & Wood, Brandon C. Carbon Incorporation and Anion Dynamics as Synergistic Drivers for Ultrafast Diffusion in Superionic LiCB11H12 and NaCB11H12. United States. doi:10.1002/aenm.201703422.
Dimitrievska, Mirjana, Shea, Patrick, Kweon, Kyoung E., Bercx, Marnik, Varley, Joel B., Tang, Wan Si, Skripov, Alexander V., Stavila, Vitalie, Udovic, Terrence J., and Wood, Brandon C. Tue . "Carbon Incorporation and Anion Dynamics as Synergistic Drivers for Ultrafast Diffusion in Superionic LiCB11H12 and NaCB11H12". United States. doi:10.1002/aenm.201703422. https://www.osti.gov/servlets/purl/1425573.
@article{osti_1425573,
title = {Carbon Incorporation and Anion Dynamics as Synergistic Drivers for Ultrafast Diffusion in Superionic LiCB11H12 and NaCB11H12},
author = {Dimitrievska, Mirjana and Shea, Patrick and Kweon, Kyoung E. and Bercx, Marnik and Varley, Joel B. and Tang, Wan Si and Skripov, Alexander V. and Stavila, Vitalie and Udovic, Terrence J. and Wood, Brandon C.},
abstractNote = {The disordered phases ofLiCB11H12 and NaCB11H12 possess superb superionic conductivities that make them suitable as solid electrolytes. In these materials, cation diffusion correlates with high orientational mobilities of the CB11H12- anions; however, the precise relationship has yet to be demonstrated. In this work, ab initio molecular dynamics and quasielastic neutron scattering are combined to probe anion reorientations and their mechanistic connection to cation mobility over a range of timescales and temperatures. It is found that anions do not rotate freely, but rather transition rapidly between orientations defined by the cation sublattice symmetry. The symmetry-breaking carbon atom in CB11H12- also plays a critical role by perturbing the energy landscape along the instantaneous orientation of the anion dipole, which couples fluctuations in the cation probability density directly to the anion motion. Anion reorientation rates exceed 3 x 1010 s-1, suggesting the underlying energy landscape fluctuates dynamically on diffusion-relevant timescales. Furthermore, carbon is found to modify the orientational preferences of the anions and aid rotational mobility, creating additional symmetry incompatibilities that inhibit ordering. The results suggest that synergy between the anion reorientational dynamics and the carbon-modified cation-anion interaction accounts for the higher ionic conductivity in CB11H12- salts compared with B12H122-.},
doi = {10.1002/aenm.201703422},
journal = {Advanced Energy Materials},
number = 8,
volume = 8,
place = {United States},
year = {2018},
month = {2}
}

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Figures / Tables:

Figure 1 Figure 1: Local repulsive carbon–cation interactions. a) Schematic of the CB11H12 − anion, showing the definitions of the angle θ relative to the C5 axis through the C atom, as well as key binding sites Ωi that describe the nearby cation distribution. b) The average distributions of Li+ (top panel)more » and Na+ (bottom panel) surrounding the CB11H12 − anions for 50 ps of AIMD at 800 K, shown as a function of θ and cation–anion radial cutoff distance r as depicted in (a). Three radial cutoffs are considered for each system. The short-range interactions are dominated by Coulombic repulsion between the cations and the C–H termination of the CB11H12 − anion and directly reflect the symmetry of the anion. Angles corresponding to sites Ωi are shown. c) The potential energy landscape associated with Li+ (top panel) and Na+ (bottom panel) as a function of distance from the anion, plotted along the angular path between the sites Ωi indicated by the black dashed line in (a). Energies are referenced to the global minimum r at Ω4.« less

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