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Understanding Superionic Conductivity in Lithium and Sodium Salts of Weakly Coordinating Closo-Hexahalocarbaborate Anions

Journal Article · · Chemistry of Materials
 [1];  [2];  [3];  [2];  [4];  [3];  [5];  [6];  [7];  [3];  [8];  [2];  [9]
  1. Aarhus Univ. (Denmark). Interdisciplinary Nanoscience Center (iNANO) and Dept. of Chemistry; Sandia National Lab. (SNL-CA), Livermore, CA (United States)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Materials Science Division
  3. Univ. of California, Riverside, CA (United States)
  4. Univ. of Antwerp (Belgium). Electron Microscopy for Materials Research
  5. Univ. of Geneva (Switzerland). DQMP, Lab. of Crystallography
  6. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)
  7. National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Maryland, College Park, MD (United States). Dept. of Materials Science and Engineering
  8. Aarhus Univ. (Denmark). Interdisciplinary Nanoscience Center (iNANO) and Dept. of Chemistry
  9. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
+ Show Author Affiliations
Solid-state ion conductors based on closo-polyborate anions combine high ionic conductivity with a rich array of tunable properties. Cation mobility in these systems is intimately related to the strength of the interaction with the neighboring anionic network and the energy for reorganizing the coordination polyhedra. In this paper, we explore such factors in solid electrolytes with two anions of the weakest coordinating ability, [HCB11H5Cl6]– and [HCB11H5Br6]–, and a total of 11 polymorphs are identified for their lithium and sodium salts. Our approach combines ab initio molecular dynamics, synchrotron X-ray powder diffraction, differential scanning calorimetry, and AC impedance measurements to investigate their structures, phase-transition behavior, anion orientational mobilities, and ionic conductivities. We find that M(HCB11H5X6) (M = Li, Na, X = Cl, Br) compounds exhibit order–disorder polymorphic transitions between 203 and 305 °C and display Li and Na superionic conductivity in the disordered state. Through detailed analysis, we illustrate how cation disordering in these compounds originates from a competitive interplay among the lattice symmetry, the anion reorientational mobility, the geometric and electronic asymmetry of the anion, and the polarizability of the halogen atoms. These factors are compared to other closo-polyborate-based ion conductors to suggest guidelines for optimizing the cation–anion interaction for fast ion mobility. This study expands the known solid-state poly(carba)borate-based materials capable of liquid-like ionic conductivities, unravels the mechanisms responsible for fast ion transport, and provides insights into the development of practical superionic solid electrolytes.
Research Organization:
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States); Sandia National Laboratories (SNL-CA), Livermore, CA (United States)
Sponsoring Organization:
Carlsberg Foundation; Danish National Research Foundation; USDOE National Nuclear Security Administration (NNSA); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Fuel Cell Technologies Office
Grant/Contract Number:
AC04-94AL85000; AC52-07NA27344; NA0003525
OSTI ID:
1646559
Alternate ID(s):
OSTI ID: 1760429
Report Number(s):
LLNL-JRNL--791101; SAND--2020-14103J; 989644
Journal Information:
Chemistry of Materials, Journal Name: Chemistry of Materials Journal Issue: 4 Vol. 32; ISSN 0897-4756
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
anions
cations
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energy – storage
group 17 compounds
inorganic
organic
physical and analytical chemistry
ionic conductivity
materials science
solid state physics