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  4. Promoting Persistent Superionic Conductivity in Sodium Monocarba-closo-dodecaborate NaCB11H12 via Confinement within Nanoporous Silica
 
research article

Promoting Persistent Superionic Conductivity in Sodium Monocarba-closo-dodecaborate NaCB11H12 via Confinement within Nanoporous Silica

Andersson, Mikael S.
•
Stavila, Vitalie
•
Skripov, Alexander, V
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August 5, 2021
Journal Of Physical Chemistry C

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 similar to 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.

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Type
research article
DOI
10.1021/acs.jpcc.1c03589
Web of Science ID

WOS:000683810700036

Author(s)
Andersson, Mikael S.
Stavila, Vitalie
Skripov, Alexander, V
Dimitrievska, Mirjana  
Psurek, Malgorzata T.
Leao, Juscelino B.
Babanova, Olga A.
Skoryunov, Roman, V
Soloninin, Alexei, V
Karlsson, Maths
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Date Issued

2021-08-05

Publisher

AMER CHEMICAL SOC

Published in
Journal Of Physical Chemistry C
Volume

125

Issue

30

Start page

16689

End page

16699

Subjects

Chemistry, Physical

•

Nanoscience & Nanotechnology

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Materials Science, Multidisciplinary

•

Chemistry

•

Science & Technology - Other Topics

•

Materials Science

•

nanoconfined libh4

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tetrahydroborate anions

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solid electrolytes

•

neutron-scattering

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ion conduction

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dynamics

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lithium

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nmr

•

reorientations

•

visualization

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LMSC1  
Available on Infoscience
August 28, 2021
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/181033
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