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Title: Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions

Abstract

Solid electrolytes with sufficiently high conductivities and stabilities are the elusive answer to the inherent shortcomings of organic liquid electrolytes prevalent in today's rechargeable batteries. We recently revealed a novel fast-ion-conducting sodium salt, Na 2B 12H 12, which contains large, icosahedral, divalent B 12H 12 2– anions that enable impressive superionic conductivity, albeit only above its 529 K phase transition. Its lithium congener, Li 2B 12H 12, possesses an even more technologically prohibitive transition temperature above 600 K. Here we show that the chemically related LiCB 11H 12 and NaCB 11H 12 salts, which contain icosahedral, monovalent CB 11H 12– anions, both exhibit much lower transition temperatures near 400 K and 380 K, respectively, and truly stellar ionic conductivities (>0.1 S cm –1) unmatched by any other known polycrystalline materials at these temperatures. Furthermore with proper modifications, we are confident that room-temperature-stabilized superionic salts incorporating such large polyhedral anion building blocks are attainable, thus enhancing their future prospects as practical electrolyte materials in next-generation, all-solid-state batteries.

Authors:
 [1];  [2];  [3];  [4];  [2];  [3];  [2];  [3]
  1. National Institute of Standards and Technology, Gaithersburg, MD (United States); Univ. of Maryland, College Park, MD (United States)
  2. Tohoku Univ., Sendai (Japan)
  3. National Institute of Standards and Technology, Gaithersburg, MD (United States)
  4. Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)
OSTI Identifier:
1327910
Report Number(s):
SAND-2016-9600J
Journal ID: ISSN 1754-5692; EESNBY; 647755
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 12; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Tang, Wan Si, Unemoto, Atsushi, Zhou, Wei, Stavila, Vitalie, Matsuo, Motoaki, Wu, Hui, Orimo, Shin-ichi, and Udovic, Terrence J. Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions. United States: N. p., 2015. Web. doi:10.1039/c5ee02941d.
Tang, Wan Si, Unemoto, Atsushi, Zhou, Wei, Stavila, Vitalie, Matsuo, Motoaki, Wu, Hui, Orimo, Shin-ichi, & Udovic, Terrence J. Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions. United States. doi:10.1039/c5ee02941d.
Tang, Wan Si, Unemoto, Atsushi, Zhou, Wei, Stavila, Vitalie, Matsuo, Motoaki, Wu, Hui, Orimo, Shin-ichi, and Udovic, Terrence J. Thu . "Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions". United States. doi:10.1039/c5ee02941d. https://www.osti.gov/servlets/purl/1327910.
@article{osti_1327910,
title = {Unparalleled lithium and sodium superionic conduction in solid electrolytes with large monovalent cage-like anions},
author = {Tang, Wan Si and Unemoto, Atsushi and Zhou, Wei and Stavila, Vitalie and Matsuo, Motoaki and Wu, Hui and Orimo, Shin-ichi and Udovic, Terrence J.},
abstractNote = {Solid electrolytes with sufficiently high conductivities and stabilities are the elusive answer to the inherent shortcomings of organic liquid electrolytes prevalent in today's rechargeable batteries. We recently revealed a novel fast-ion-conducting sodium salt, Na2B12H12, which contains large, icosahedral, divalent B12H122– anions that enable impressive superionic conductivity, albeit only above its 529 K phase transition. Its lithium congener, Li2B12H12, possesses an even more technologically prohibitive transition temperature above 600 K. Here we show that the chemically related LiCB11H12 and NaCB11H12 salts, which contain icosahedral, monovalent CB11H12– anions, both exhibit much lower transition temperatures near 400 K and 380 K, respectively, and truly stellar ionic conductivities (>0.1 S cm–1) unmatched by any other known polycrystalline materials at these temperatures. Furthermore with proper modifications, we are confident that room-temperature-stabilized superionic salts incorporating such large polyhedral anion building blocks are attainable, thus enhancing their future prospects as practical electrolyte materials in next-generation, all-solid-state batteries.},
doi = {10.1039/c5ee02941d},
journal = {Energy & Environmental Science},
number = 12,
volume = 8,
place = {United States},
year = {2015},
month = {10}
}

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Works referenced in this record:

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    Works referencing / citing this record:

    CCDC 1872755: Experimental Crystal Structure Determination: TIMTUH : lithium 1-carba-closo-dodecaborate(12)
    dataset, September 2018


    CCDC 1875418: Experimental Crystal Structure Determination: WIPQIY : sodium carbadodecaborate
    dataset, September 2018