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Title: Stabilizing Superionic-Conducting Structures via Mixed-Anion Solid Solutions of Monocarba- closo -borate Salts

Abstract

Solid lithium and sodium closo-polyborate-based salts are capable of superionic conductivities surpassing even liquid electrolytes, but often only at above-ambient temperatures where their entropically driven disordered phases become stabilized. Here we show by X-ray diffraction, quasielastic neutron scattering, differential scanning calorimetry, NMR, and AC impedance measurements that by introducing 'geometric frustration' via the mixing of two different closo-polyborate anions, namely, 1-CB9H10- and CB11H12-, to form solid-solution anion-alloy salts of lithium or sodium, we can successfully suppress the formation of possible ordered phases in favor of disordered, fast-ion-conducting alloy phases over a broad temperature range from subambient to high temperatures. Finally, this result exemplifies an important advancement for further improving on the remarkable conductive properties generally displayed by this class of materials and represents a practical strategy for creating tailored, ambient-temperature, solid, superionic conductors for a variety of upcoming all-solid-state energy devices of the future.

Authors:
 [1];  [2];  [3];  [3];  [3];  [3];  [4];  [5];  [6];  [7]
  1. NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, United States, Department of Materials Science and Engineering, University of Maryland, College Park, Maryland 20742-2115, United States
  2. Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
  3. Institute of Metal Physics, Ural Branch of the Russian Academy of Sciences, Ekaterinburg 620990, Russia
  4. NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, United States, National Renewable Energy Laboratory, Golden, Colorado 80401, United States
  5. Energy Nanomaterials, Sandia National Laboratories, Livermore, California 94551, United States
  6. Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan, WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan
  7. NIST Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-6102, United States
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Sustainable Transportation Office. Hydrogen Fuel Cell Technologies Office; National Science Foundation (NSF)
OSTI Identifier:
1315853
Alternate Identifier(s):
OSTI ID: 1345722
Report Number(s):
NREL/JA-5900-68062
Journal ID: ISSN 2380-8195
Grant/Contract Number:  
AC36-08GO28308; AC04-94AL85000; DMR-0944772; 25220911; 15-03- 01114; 26820311
Resource Type:
Published Article
Journal Name:
ACS Energy Letters
Additional Journal Information:
Journal Name: ACS Energy Letters Journal Volume: 1 Journal Issue: 4; Journal ID: ISSN 2380-8195
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; superionic conductivities; anions; ordered phases; disorder

Citation Formats

Tang, Wan Si, Yoshida, Koji, Soloninin, Alexei V., Skoryunov, Roman V., Babanova, Olga A., Skripov, Alexander V., Dimitrievska, Mirjana, Stavila, Vitalie, Orimo, Shin-ichi, and Udovic, Terrence J. Stabilizing Superionic-Conducting Structures via Mixed-Anion Solid Solutions of Monocarba- closo -borate Salts. United States: N. p., 2016. Web. doi:10.1021/acsenergylett.6b00310.
Tang, Wan Si, Yoshida, Koji, Soloninin, Alexei V., Skoryunov, Roman V., Babanova, Olga A., Skripov, Alexander V., Dimitrievska, Mirjana, Stavila, Vitalie, Orimo, Shin-ichi, & Udovic, Terrence J. Stabilizing Superionic-Conducting Structures via Mixed-Anion Solid Solutions of Monocarba- closo -borate Salts. United States. https://doi.org/10.1021/acsenergylett.6b00310
Tang, Wan Si, Yoshida, Koji, Soloninin, Alexei V., Skoryunov, Roman V., Babanova, Olga A., Skripov, Alexander V., Dimitrievska, Mirjana, Stavila, Vitalie, Orimo, Shin-ichi, and Udovic, Terrence J. Fri . "Stabilizing Superionic-Conducting Structures via Mixed-Anion Solid Solutions of Monocarba- closo -borate Salts". United States. https://doi.org/10.1021/acsenergylett.6b00310.
@article{osti_1315853,
title = {Stabilizing Superionic-Conducting Structures via Mixed-Anion Solid Solutions of Monocarba- closo -borate Salts},
author = {Tang, Wan Si and Yoshida, Koji and Soloninin, Alexei V. and Skoryunov, Roman V. and Babanova, Olga A. and Skripov, Alexander V. and Dimitrievska, Mirjana and Stavila, Vitalie and Orimo, Shin-ichi and Udovic, Terrence J.},
abstractNote = {Solid lithium and sodium closo-polyborate-based salts are capable of superionic conductivities surpassing even liquid electrolytes, but often only at above-ambient temperatures where their entropically driven disordered phases become stabilized. Here we show by X-ray diffraction, quasielastic neutron scattering, differential scanning calorimetry, NMR, and AC impedance measurements that by introducing 'geometric frustration' via the mixing of two different closo-polyborate anions, namely, 1-CB9H10- and CB11H12-, to form solid-solution anion-alloy salts of lithium or sodium, we can successfully suppress the formation of possible ordered phases in favor of disordered, fast-ion-conducting alloy phases over a broad temperature range from subambient to high temperatures. Finally, this result exemplifies an important advancement for further improving on the remarkable conductive properties generally displayed by this class of materials and represents a practical strategy for creating tailored, ambient-temperature, solid, superionic conductors for a variety of upcoming all-solid-state energy devices of the future.},
doi = {10.1021/acsenergylett.6b00310},
journal = {ACS Energy Letters},
number = 4,
volume = 1,
place = {United States},
year = {Fri Sep 02 00:00:00 EDT 2016},
month = {Fri Sep 02 00:00:00 EDT 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1021/acsenergylett.6b00310

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