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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: 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:
 [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.:
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:
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. https://doi.org/10.1002/aenm.201500096
Thompson, Travis, Sharafi, Asma, Johannes, Michelle D., Huq, Ashfia, Allen, Jan L., Wolfenstine, Jeff, and Sakamoto, Jeff. 2015. "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},
url = {https://www.osti.gov/biblio/1356887}, journal = {Advanced Energy Materials},
issn = {1614-6832},
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: 129 works
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Works referenced in this record:

Optimizing Li+ conductivity in a garnet framework
journal, January 2012


Measurement of Hall mobilites in AgPO$z.sbnd;AgI glasses
journal, September 1988


Switching on Fast Lithium Ion Conductivity in Garnets: The Structure and Transport Properties of Li 3+ x Nd 3 Te 2− x Sb x O 12
journal, March 2008


Challenges for Rechargeable Li Batteries
journal, February 2010


From order to disorder: The structure of lithium-conducting garnets Li7−xLa3TaxZr2−xO12 (x=0–2)
journal, January 2012


Optimum lithium-ion conductivity in cubic Li7−xLa3Hf2−xTaxO12
journal, July 2012


Hall Effect of Silver Ions in Rb Ag 4 I 5 Single Crystals
journal, October 1972


Crystal structures of La3Li5M2O12 (M=Nb, Ta)
journal, October 1988


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


On the thermodynamic properties of the solid electrolyte RbAg4I5
journal, March 1969


Lithium ionic jump motion in the fast solid ion conductor
journal, July 2008


Concerted Migration Mechanism in the Li Ion Dynamics of Garnet-Type Li 7 La 3 Zr 2 O 12
journal, January 2013


Ionic Hall effect measured in rubidium silver iodide
journal, December 2002


Fabrication of all-solid-state lithium battery with lithium metal anode using Al2O3-added Li7La3Zr2O12 solid electrolyte
journal, September 2011


Ionic Hall effect in crystals: Independent versus cooperative hopping in AgBr and α-AgI
journal, May 1990


Electroceramics: Characterization by Impedance Spectroscopy
journal, March 1990


Structure and dynamics of the fast lithium ion conductor “Li7La3Zr2O12”
journal, January 2011


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


Charge carrier mobility and concentration as a function of composition in AgPO 3 –AgI glasses
journal, December 2011

  • Rodrigues, Ana Candida Martins; Nascimento, Marcio Luis Ferreira; Bragatto, Caio Barca
  • The Journal of Chemical Physics, Vol. 135, Issue 23
  • https://doi.org/10.1063/1.3666835

DFT Study of the Role of Al 3+ in the Fast Ion-Conductor Li 7–3 x Al 3+ x La 3 Zr 2 O 12 Garnet
journal, April 2014


Origin of the Structural Phase Transition in Li 7 La 3 Zr 2 O 12
journal, November 2012


Lithium dimer formation in the Li-conducting garnets Li 5+x Ba x La 3−x Ta 2 O 12 (0 < x ≤ 1.6)
journal, January 2007


Effect of Simultaneous Substitution of Alkali Earth Metals and Nb in Li7La3Zr2O12 on Lithium-Ion Conductivity
journal, January 2013


Relationship between morphology and conductivity of block-copolymer based battery separators
journal, March 2012


Li6ALa2Ta2O12 (A = Sr, Ba): Novel Garnet-Like Oxides for Fast Lithium Ion Conduction
journal, January 2005


Synthesis of garnet-type Li7−xLa3Zr2O12−1/2x and its stability in aqueous solutions
journal, February 2011


Li7-xLa3Sn2-xNbxO12 (x=0.25–1) cubic lithium garnet
journal, June 2012


Tetragonal vs. cubic phase stability in Al – free Ta doped Li 7 La 3 Zr 2 O 12 (LLZO)
journal, January 2014


EXPGUI , a graphical user interface for GSAS
journal, April 2001


Heat Capacity, Transformations, and Thermal Disorder in the Solid Electrolyte RbAg 4 I 5
journal, November 1969


Low temperature stabilization of cubic (Li7−xAlx/3)La3Zr2O12: role of aluminum during formation
journal, January 2013


Synthesis and Crystal Chemistry of the Fast Li-Ion Conductor Li 7 La 3 Zr 2 O 12 Doped with Fe
journal, July 2013


Structure and Li+ dynamics of Sb-doped Li7La3Zr2O12 fast lithium ion conductors
journal, January 2013


The mechanism of Li-ion transport in the garnet Li 5 La 3 Nb 2 O 12
journal, January 2007


The structure of the lithium-rich garnets Li6SrLa2M2O12 and Li6.4Sr1.4La1.6M2O12 (M=Sb, Ta)
journal, April 2008


The use of 6 Li{ 7 Li}-REDOR NMR spectroscopy to compare the ionic conductivities of solid-state lithium ion electrolytes
journal, January 2014


Building better batteries
journal, February 2008


High Ionic Conductivity Lithium Garnet Oxides of Li7−xLa3Zr2−xTaxO12 Compositions
journal, January 2012


Li 6 La 3 SnMO 12 (M = Sb, Nb, Ta), a Family of Lithium Garnets with High Li-Ion Conductivity
journal, January 2012


Li diffusive behavior of garnet-type oxides studied by muon-spin relaxation and QENS
journal, September 2014


Mechanisms of Li + transport in garnet-type cubic Li 3 + x La 3 M 2 O 12 ( M = Te, Nb, Zr)
journal, February 2012


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


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


Solid-State Electrolytes: Revealing the Mechanisms of Li-Ion Conduction in Tetragonal and Cubic LLZO by First-Principles Calculations
journal, March 2014


Synthesis and properties of Al-free Li7−xLa3Zr2−xTaxO12 garnet related oxides
journal, September 2014


A neutron diffraction study of the d0 and d10 lithium garnets Li3Nd3W2O12 and Li5La3Sb2O12
journal, June 2007


Ionic Hall effect measured in rubidium silver iodide
journal, January 2001


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


On the thermodynamic properties of the solid electrolyte RbAg4I5
journal, December 1968


Hall Effect of Silver Ions in Rb Ag 4 I 5 Single Crystals
journal, May 1974


Structure and dynamics of the fast lithium ion conductor "li 7La3Zr2O12"
text, January 2011


Lithium Dimer Formation in the Li-Conducting Garnets Li5+xBaxLa3-xTa2O12 (0 < x ≤ 1.6).
journal, August 2007


Works referencing / citing this record:

Dopant‐Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal
journal, January 2019


Transient Behavior of the Metal Interface in Lithium Metal-Garnet Batteries
journal, October 2017


Neutron Instruments for Research in Coordination Chemistry: Neutron Instruments for Research in Coordination Chemistry
journal, January 2019


Negating interfacial impedance in garnet-based solid-state Li metal batteries
journal, December 2016


Lattice-geometry effects in garnet solid electrolytes: a lattice-gas Monte Carlo simulation study
journal, November 2017


Transient Behavior of the Metal Interface in Lithium Metal-Garnet Batteries
journal, October 2017


Electrochemical Stability of Li6.5La3Zr1.5M0.5O12 (M = Nb or Ta) against Metallic Lithium
journal, May 2016