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Title: Carbon Incorporation and Anion Dynamics as Synergistic Drivers for Ultrafast Diffusion in Superionic LiCB11H12 and NaCB11H12

Journal Article · · Advanced Energy Materials
 [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)
+ Show Author Affiliations

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-.

Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Hydrogen and Fuel Cell Technologies Program (EE-3F)
Grant/Contract Number:
AC36-08GO28308
OSTI ID:
1425573
Alternate ID(s):
OSTI ID: 1542730; OSTI ID: 1422013
Report Number(s):
NREL/JA-5900-71080
Journal Information:
Advanced Energy Materials, Journal Name: Advanced Energy Materials Journal Issue: 8 Vol. 8; ISSN 1614-6832
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (7)

A complex hydride lithium superionic conductor for high-energy-density all-solid-state lithium metal batteries journal March 2019
Electronic shell structures, self-trapped excitons, and defect-bound excitons in Li 2 B 12 H 12 journal January 2019
Dynamics of porous and amorphous magnesium borohydride to understand solid state Mg-ion-conductors journal June 2020
Dynamics of porous and amorphous magnesium borohydride to understand solid state Mg-ion-conductors text January 2020
Fundamentals of inorganic solid-state electrolytes for batteries journal August 2019
Sur-/interfacial regulation in all-solid-state rechargeable Li-ion batteries based on inorganic solid-state electrolytes: advances and perspectives journal January 2019
Lightweight complex metal hydrides for Li-, Na-, and Mg-based batteries journal March 2019

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Related Subjects

36 MATERIALS SCIENCE
ab initio molecular dynamics
closo-borates
quasielastic neutron scattering
solid electrolytes
superionic