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Title: A tale of two sites: On defining the carrier concentration in garnet-based ionic conductors for advanced Li batteries

Abstract

Solid electrolytes based on the garnet crystal structure have recently been identified as a promising material to enable advance Li battery cell chemistries because of the unprecedented combination of high ionic conductivity and electrochemical stability against metallic Li. To better understand the mechanisms that give rise to high conductivity, the goal of this work is to correlate Li site occupancy with Li-ion transport. Toward this goal, the Li site occupancy is studied in cubic garnet as a function of Li concentration over the compositions range: Li 7-xLa 3Zr 2-xTa xO 12 (x = 0.5, 0.75, and 1.5). The distribution of Li between the two interstitial sites (24d and 96h) is determined using neutron and synchrotron diffraction. The bulk conductivity is measured on >97% relative density polycrystalline specimens to correlate Li-ion transport as a function of Li site occupancy. It is determined that the conductivity changes nonlinearly with the occupancy of the octahedral (96h) Li site. It is shown that the effective carrier concentration is dependent on the Li site occupancy and suggests that this is a consequence of significant carrier-carrier coulombic interactions. Moreover, the observation of maximum conductivity near Li = 6.5 mol is explained.

Authors:
 [1];  [1];  [2];  [3];  [4];  [4];  [1]
  1. Univ. of Michigan, Ann Arbor, MI (United States)
  2. Naval Research Lab., Anacostia, VA (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  4. Army Research Lab., Adelphi, MD (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1356887
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Advanced Energy Materials
Additional Journal Information:
Journal Volume: 5; Journal Issue: 11; Journal ID: ISSN 1614-6832
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 25 ENERGY STORAGE; batteries; garnet; ionic conductivity; neutron diffraction; solid electrolytes; rubidium silver-iodide; solide-electrolyte; Lithium garnets; alpha-AGI; conductivity; LI7LA3ZR2O12; disorder; oxides; SB; AL

Citation Formats

Thompson, Travis, Sharafi, Asma, Johannes, Michelle D., Huq, Ashfia, Allen, Jan L., Wolfenstine, Jeff, and Sakamoto, Jeff. A tale of two sites: On defining the carrier concentration in garnet-based ionic conductors for advanced Li batteries. United States: N. p., 2015. Web. doi:10.1002/aenm.201500096.
Thompson, Travis, Sharafi, Asma, Johannes, Michelle D., Huq, Ashfia, Allen, Jan L., Wolfenstine, Jeff, & Sakamoto, Jeff. A tale of two sites: On defining the carrier concentration in garnet-based ionic conductors for advanced Li batteries. United States. doi:10.1002/aenm.201500096.
Thompson, Travis, Sharafi, Asma, Johannes, Michelle D., Huq, Ashfia, Allen, Jan L., Wolfenstine, Jeff, and Sakamoto, Jeff. Sat . "A tale of two sites: On defining the carrier concentration in garnet-based ionic conductors for advanced Li batteries". United States. doi:10.1002/aenm.201500096. https://www.osti.gov/servlets/purl/1356887.
@article{osti_1356887,
title = {A tale of two sites: On defining the carrier concentration in garnet-based ionic conductors for advanced Li batteries},
author = {Thompson, Travis and Sharafi, Asma and Johannes, Michelle D. and Huq, Ashfia and Allen, Jan L. and Wolfenstine, Jeff and Sakamoto, Jeff},
abstractNote = {Solid electrolytes based on the garnet crystal structure have recently been identified as a promising material to enable advance Li battery cell chemistries because of the unprecedented combination of high ionic conductivity and electrochemical stability against metallic Li. To better understand the mechanisms that give rise to high conductivity, the goal of this work is to correlate Li site occupancy with Li-ion transport. Toward this goal, the Li site occupancy is studied in cubic garnet as a function of Li concentration over the compositions range: Li7-xLa3Zr2-xTaxO12 (x = 0.5, 0.75, and 1.5). The distribution of Li between the two interstitial sites (24d and 96h) is determined using neutron and synchrotron diffraction. The bulk conductivity is measured on >97% relative density polycrystalline specimens to correlate Li-ion transport as a function of Li site occupancy. It is determined that the conductivity changes nonlinearly with the occupancy of the octahedral (96h) Li site. It is shown that the effective carrier concentration is dependent on the Li site occupancy and suggests that this is a consequence of significant carrier-carrier coulombic interactions. Moreover, the observation of maximum conductivity near Li = 6.5 mol is explained.},
doi = {10.1002/aenm.201500096},
journal = {Advanced Energy Materials},
number = 11,
volume = 5,
place = {United States},
year = {Sat Mar 21 00:00:00 EDT 2015},
month = {Sat Mar 21 00:00:00 EDT 2015}
}

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Cited by: 32 works
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Works referenced in this record:

High lithium ionic conductivity in the garnet-type oxide Li7−XLa3(Zr2−X, NbX)O12 (X=0–2)
journal, March 2011


Effect of substitution (Ta, Al, Ga) on the conductivity of Li7La3Zr2O12
journal, May 2012


Fast Lithium Ion Conduction in Garnet-Type Li7La3Zr2O12
journal, October 2007

  • Murugan, Ramaswamy; Thangadurai, Venkataraman; Weppner, Werner
  • Angewandte Chemie International Edition, Vol. 46, Issue 41, p. 7778-7781
  • DOI: 10.1002/anie.200701144

Building better batteries
journal, February 2008

  • Armand, M.; Tarascon, J.-M.
  • Nature, Vol. 451, Issue 7179, p. 652-657
  • DOI: 10.1038/451652a

Li–O2 and Li–S batteries with high energy storage
journal, January 2012

  • Bruce, Peter G.; Freunberger, Stefan A.; Hardwick, Laurence J.
  • Nature Materials, Vol. 11, Issue 1, p. 19-29
  • DOI: 10.1038/nmat3191

The role of Al and Li concentration on the formation of cubic garnet solid electrolyte of nominal composition Li7La3Zr2O12
journal, January 2012

  • Rangasamy, Ezhiyl; Wolfenstine, Jeff; Sakamoto, Jeffrey
  • Solid State Ionics, Vol. 206, p. 28-32
  • DOI: 10.1016/j.ssi.2011.10.022