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Promoting Persistent Superionic Conductivity in Sodium Monocarba-closo-dodecaborate NaCB11H12 via Confinement within Nanoporous Silica.
Andersson, Mikael S; Stavila, Vitalie; Skripov, Alexander V; Dimitrievska, Mirjana; Psurek, Malgorzata T; Leão, Juscelino B; Babanova, Olga A; Skoryunov, Roman V; Soloninin, Alexei V; Karlsson, Maths; Udovic, Terrence J.
Afiliación
  • Andersson MS; Department of Chemistry and Chemical Engineering, Chalmers University of Technology, SE-412 96 Göteborg, Sweden.
  • Stavila V; Department of Chemistry, Ångström Laboratory, Uppsala University, Box 538, 75121 Uppsala, Sweden.
  • Skripov AV; NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, United States.
  • Dimitrievska M; Energy Nanomaterials, Sandia National Laboratories, Livermore, California 94551, United States.
  • Psurek MT; Institute of Metal Physics, Ural Branch of the Russian Academy of Sciences, Ekaterinburg 620108, Russia.
  • Leão JB; NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, United States.
  • Babanova OA; National Renewable Energy Laboratory, Golden, Colorado 80401, United States.
  • Skoryunov RV; Laboratory of Semiconductor Materials, Institute of Materials, Ecole Polytechnique Fédérale de Lausanne, 1015 Lausanne, Switzerland.
  • Soloninin AV; NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, United States.
  • Karlsson M; Department of Chemistry, University of Maryland, College Park, Maryland 20742, United States.
  • Udovic TJ; NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, United States.
J Phys Chem C Nanomater Interfaces ; 125(30): 16689-16699, 2021 Aug 05.
Article en En | MEDLINE | ID: mdl-34476037
Superionic phases of bulk anhydrous salts based on large cluster-like polyhedral (carba)borate anions are generally stable only well above room temperature, rendering them unsuitable as solid-state electrolytes in energy-storage devices that typically operate at close to room temperature. To unlock their technological potential, strategies are needed to stabilize these superionic properties down to subambient temperatures. One such strategy involves altering the bulk properties by confinement within nanoporous insulators. In the current study, the unique structural and ion dynamical properties of an exemplary salt, NaCB11H12, nanodispersed within porous, high-surface-area silica via salt-solution infiltration were studied by differential scanning calorimetry, X-ray powder diffraction, neutron vibrational spectroscopy, nuclear magnetic resonance, quasielastic neutron scattering, and impedance spectroscopy. Combined results hint at the formation of a nanoconfined phase that is reminiscent of the high-temperature superionic phase of bulk NaCB11H12, with dynamically disordered CB11H12 - anions exhibiting liquid-like reorientational mobilities. However, in contrast to this high-temperature bulk phase, the nanoconfined NaCB11H12 phase with rotationally fluid anions persists down to cryogenic temperatures. Moreover, the high anion mobilities promoted fast-cation diffusion, yielding Na+ superionic conductivities of ∼0.3 mS/cm at room temperature, with higher values likely attainable via future optimization. It is expected that this successful strategy for conductivity enhancement could be applied as well to other related polyhedral (carba)borate-based salts. Thus, these results present a new route to effectively utilize these types of superionic salts as solid-state electrolytes in future battery applications.

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Phys Chem C Nanomater Interfaces Año: 2021 Tipo del documento: Article País de afiliación: Suecia Pais de publicación: Estados Unidos

Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: J Phys Chem C Nanomater Interfaces Año: 2021 Tipo del documento: Article País de afiliación: Suecia Pais de publicación: Estados Unidos