DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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)

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

References (46)

Unified Approach for Molecular Dynamics and Density-Functional Theory journal November 1985
Basis Set Exchange:  A Community Database for Computational Sciences journal March 2007
The least coordinating anion journal May 1986
Update 1 of: Chemistry of the Carba- closo -dodecaborate(−) Anion, CB 11 H 12 journal August 2013
Halogenated Sodium- closo -Dodecaboranes as Solid-State Ion Conductors text January 2017
Complex Hydrides for Electrochemical Energy Storage journal January 2014
Cation reduction and comproportionation as novel strategies to produce high voltage, halide free, carborane based electrolytes for rechargeable Mg batteries journal January 2015
Superhalogens as Building Blocks of Halogen-Free Electrolytes in Lithium-Ion Batteries journal October 2014
Liquid‐Like Ionic Conduction in Solid Lithium and Sodium Monocarba‐ closo ‐Decaborates Near or at Room Temperature journal February 2016
An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries journal May 2015
NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations journal September 2010
An Efficient Halogen-Free Electrolyte for Use in Rechargeable Magnesium Batteries journal May 2015
The role of databases in support of computational chemistry calculations journal October 1996
Structural, Chemical, and Dynamical Frustration: Origins of Superionic Conductivity in closo -Borate Solid Electrolytes journal October 2017
Sodium superionic conduction in Na 2 B 12 H 12 journal January 2014
Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions journal January 2015
Nosé–Hoover chains: The canonical ensemble via continuous dynamics journal August 1992
Order–Disorder Transitions and Superionic Conductivity in the Sodium nido -Undeca(carba)borates journal November 2017
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
Understanding Ionic Conductivity Trends in Polyborane Solid Electrolytes from Ab Initio Molecular Dynamics journal December 2016
n Moldyn: A program package for a neutron scattering oriented analysis of molecular dynamics simulations journal March 2003
The Disk Chopper Spectrometer at NIST: a new instrument for quasielastic neutron scattering studies journal August 2003
Exceptional Superionic Conductivity in Disordered Sodium Decahydro- closo -decaborate journal October 2014
QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials journal September 2009
The renaissance of hydrides as energy materials journal December 2016
Superionic glass-ceramic electrolytes for room-temperature rechargeable sodium batteries journal January 2012
The structure of monoclinic Na 2 B 10 H 10 : a combined diffraction, spectroscopy, and theoretical approach journal January 2015
Carboranes other than C2B10H12 journal March 1992
nMOLDYN: A program package for a neutron scattering oriented analysis of Molecular Dynamics simulations journal September 1995
Carboranes:  A New Class of Weakly Coordinating Anions for Strong Electrophiles, Oxidants, and Superacids journal March 1998
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
DAVE: A Comprehensive Software Suite for the Reduction, Visualization, and Analysis of Low Energy Neutron Spectroscopic Data
  • Azuah, Richard Tumanjong; Kneller, Larry R.; Qiu, Yiming
  • Journal of Research of the National Institute of Standards and Technology, Vol. 114, Issue 6 https://doi.org/10.6028/jres.114.025
journal November 2009
One-dimensional intergrowths in two-dimensional zeolite nanosheets and their effect on ultra-selective transport journal February 2020
Generalized Gradient Approximation Made Simple journal October 1996
Anion Reorientations in the Superionic Conducting Phase of Na 2 B 12 H 12 journal July 2014
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 journal December 2016
Optimized pseudopotentials journal January 1990
Superhalogens as Building Blocks of Halogen-Free Electrolytes in Lithium-Ion Batteries journal October 2014
Metal Borohydrides as Electrolytes for Solid-State Li, Na, Mg, and Ca Batteries: A First-Principles Study journal October 2017
Diffusion in periodic potentials journal June 1977
Complex high-temperature phase transitions in Li2B12H12 and Na2B12H12 journal April 2014
Halogenated Sodium- closo -Dodecaboranes as Solid-State Ion Conductors journal April 2017
Stabilizing Superionic-Conducting Structures via Mixed-Anion Solid Solutions of Monocarba- closo -borate Salts journal September 2016
Stabilizing lithium and sodium fast-ion conduction in solid polyhedral-borate salts at device-relevant temperatures journal July 2016
Fast sodium ionic conduction in Na 2 B 10 H 10 -Na 2 B 12 H 12 pseudo-binary complex hydride and application to a bulk-type all-solid-state battery journal March 2017
Structural origin of the superionic Na conduction in Na 2 B 10 H 10 closo-borates and enhanced conductivity by Na deficiency for high performance solid electrolytes journal January 2016

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