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: 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.
- Authors:
-
- Univ. of Michigan, Ann Arbor, MI (United States)
- Naval Research Lab., Anacostia, VA (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Army Research Lab., Adelphi, MD (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Revolutionary Materials for Solid State Energy Conversion (RMSSEC); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1356887
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- 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. https://doi.org/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. https://doi.org/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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