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

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.

doi:10.1002/aenm.201703422

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

Journal Article · 20 February 2018 · Advanced Energy Materials

DOI: https://doi.org/10.1002/aenm.201703422 · OSTI ID:1425573

Dimitrievska, Mirjana ^[1]; Shea, Patrick ^[2]; Kweon, Kyoung E. ^[2]; Bercx, Marnik ^[3]; Varley, Joel B. ^[2]; Tang, Wan Si ^[1]; Skripov, Alexander V. ^[4]; Stavila, Vitalie ^[5]; Udovic, Terrence J. ^[6];

^[2]

National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States); Univ. of Maryland, College Park, MD (United States)
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Univ. of Antwerp (Belgium)
Ural Division of the Russian Academy of Sciences, Ekaterinburg (Russian Federation)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)

Abstract The disordered phases of LiCB ₁₁ H ₁₂ and NaCB ₁₁ H 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 ₁₁ H 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 ₁₁ H 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 × 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 the higher ionic conductivity in CB ₁₁ H ₁₂ ⁻ salts compared with B ₁₂ H ₁₂ ²⁻ .

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Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States); Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Hydrogen and Fuel Cell Technologies Program (EE-3F); USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC36-08GO28308; DE‐AC52‐07NA27344; DE‐AC36‐08GO28308; DE‐AC04‐94AL85000; AC52-07NA27344

OSTI ID:: 1425573

Alternate ID(s):: OSTI ID: 1422013; OSTI ID: 1542730

Report Number(s):: NREL/JA-5900-71080; LLNL-JRNL-740042; TRN: US1802123

Journal Information:: Advanced Energy Materials, Vol. 8, Issue 8; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 63 works

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