Bi aliovalent substitution in Li7La3Zr2O12 garnets: Structural and ionic conductivity effects
Abstract
We report on the synthesis of cubic-phase garnet-type solid-state electrolytes based on Bi-doped Li7La3Zr2O12 (LLZO). Bi aliovalent substitution of Zr in LLZO utilizing the Pechini processing method is employed to synthesize Li7-xLa3Zr2-xBixO12 compounds. A strong dependence of the ionic conductivity on Bi content is observed, and under our synthesis and sintering conditions, a >100-fold increase over the un-doped sample is observed for x=0.75. Cubic-phase Li6La3Zr1BiO12 compounds are generated upon annealing in air in the temperature range 650 °C-900 °C. In contrast, in the absence of Bi, the cubic garnet phase of Li7La3Zr2O12 is not formed below 700 °C and a transformation to the tetragonal phase is observed at similar to 900 °C for this un-doped compound. The role of Bi in lowering the formation temperature of the garnet cubic phase and in the ionic conductivity improvements is investigated in this work. We ascribe the effect of Bi-doping on ionic conductivity increments to changes in Li+-site occupancy and lattice parameters and the reduction in the formation temperature for the cubic-phase formation to rate enhancements of the solid-state reaction. To identify the site occupancy of Bi in the garnet structure, we employ synchrotron extended x-ray absorption fine structure spectroscopy. Our results indicatemore »
- Authors:
-
[2];
[1];
[1]
- Purdue Univ., West Lafayette, IN (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Joint Center for Energy Storage Research (JCESR)
- OSTI Identifier:
- 1647159
- Alternate Identifier(s):
- OSTI ID: 1602333
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- AIP Advances
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 3; Journal ID: ISSN 2158-3226
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Sintering; crystalline properties; ceramic materials; synchrotrons; ionic conductivity; scanning electron microscopy; X-ray absorption spectroscopy; solgels; electrolytes; batteries
Citation Formats
Schwanz, Derek K., Villa, Andres, Balasubramanian, Mahalingam, Helfrecht, Benjamin A., and Marinero, Ernesto E. Bi aliovalent substitution in Li7La3Zr2O12 garnets: Structural and ionic conductivity effects. United States: N. p., 2020.
Web. doi:10.1063/1.5141764.
Schwanz, Derek K., Villa, Andres, Balasubramanian, Mahalingam, Helfrecht, Benjamin A., & Marinero, Ernesto E. Bi aliovalent substitution in Li7La3Zr2O12 garnets: Structural and ionic conductivity effects. United States. https://doi.org/10.1063/1.5141764
Schwanz, Derek K., Villa, Andres, Balasubramanian, Mahalingam, Helfrecht, Benjamin A., and Marinero, Ernesto E. Mon .
"Bi aliovalent substitution in Li7La3Zr2O12 garnets: Structural and ionic conductivity effects". United States. https://doi.org/10.1063/1.5141764. https://www.osti.gov/servlets/purl/1647159.
@article{osti_1647159,
title = {Bi aliovalent substitution in Li7La3Zr2O12 garnets: Structural and ionic conductivity effects},
author = {Schwanz, Derek K. and Villa, Andres and Balasubramanian, Mahalingam and Helfrecht, Benjamin A. and Marinero, Ernesto E.},
abstractNote = {We report on the synthesis of cubic-phase garnet-type solid-state electrolytes based on Bi-doped Li7La3Zr2O12 (LLZO). Bi aliovalent substitution of Zr in LLZO utilizing the Pechini processing method is employed to synthesize Li7-xLa3Zr2-xBixO12 compounds. A strong dependence of the ionic conductivity on Bi content is observed, and under our synthesis and sintering conditions, a >100-fold increase over the un-doped sample is observed for x=0.75. Cubic-phase Li6La3Zr1BiO12 compounds are generated upon annealing in air in the temperature range 650 °C-900 °C. In contrast, in the absence of Bi, the cubic garnet phase of Li7La3Zr2O12 is not formed below 700 °C and a transformation to the tetragonal phase is observed at similar to 900 °C for this un-doped compound. The role of Bi in lowering the formation temperature of the garnet cubic phase and in the ionic conductivity improvements is investigated in this work. We ascribe the effect of Bi-doping on ionic conductivity increments to changes in Li+-site occupancy and lattice parameters and the reduction in the formation temperature for the cubic-phase formation to rate enhancements of the solid-state reaction. To identify the site occupancy of Bi in the garnet structure, we employ synchrotron extended x-ray absorption fine structure spectroscopy. Our results indicate that Bi additions occupy the Zr-type sites exclusively, to within the accuracy of the measurements.},
doi = {10.1063/1.5141764},
journal = {AIP Advances},
number = 3,
volume = 10,
place = {United States},
year = {Mon Mar 02 00:00:00 EST 2020},
month = {Mon Mar 02 00:00:00 EST 2020}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 11 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
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
- O'Callaghan, Michael P.; Cussen, Edmund J.
- Chem. Commun., Issue 20
Optimizing Li+ conductivity in a garnet framework
journal, January 2012
- Li, Yutao; Han, Jian- Tao; Wang, Chang- An
- Journal of Materials Chemistry, Vol. 22, Issue 30
Studies on Capacity Fade of Spinel-Based Li-Ion Batteries
journal, January 2002
- Premanand, Ramadass; Durairajan, Anand; Haran, Bala
- Journal of The Electrochemical Society, Vol. 149, Issue 1
Synthesis, Crystal Structure, and Stability of Cubic Li 7– x La 3 Zr 2– x Bi x O 12
journal, November 2016
- Wagner, Reinhard; Rettenwander, Daniel; Redhammer, Günther J.
- Inorganic Chemistry, Vol. 55, Issue 23
Structure and Stoichiometry in Supervalent Doped Li 7 La 3 Zr 2 O 12
journal, May 2015
- Mukhopadhyay, Saikat; Thompson, Travis; Sakamoto, Jeff
- Chemistry of Materials, Vol. 27, Issue 10
Origin of the Structural Phase Transition in
journal, November 2012
- Bernstein, N.; Johannes, M. D.; Hoang, Khang
- Physical Review Letters, Vol. 109, Issue 20
Synthesis of garnet-type Li7−xLa3Zr2O12−1/2x and its stability in aqueous solutions
journal, February 2011
- Shimonishi, Yuta; Toda, Akiharu; Zhang, Tao
- Solid State Ionics, Vol. 183, Issue 1
Sol–gel synthesis and lithium ion conductivity of Li7La3Zr2O12 with garnet-related type structure
journal, March 2011
- Kokal, I.; Somer, M.; Notten, P. H. L.
- Solid State Ionics, Vol. 185, Issue 1
Issues and challenges facing rechargeable lithium batteries
journal, November 2001
- Tarascon, J.-M.; Armand, M.
- Nature, Vol. 414, Issue 6861, p. 359-367
Solid state lithium ion conductors: Design considerations by thermodynamic approach
journal, May 2002
- Thangadurai, V.; Weppner, W.
- Ionics, Vol. 8, Issue 3-4
Simple method to determine electronic and ionic components of the conductivity in mixed conductors a review
journal, May 2002
- Huggins, R. A.
- Ionics, Vol. 8, Issue 3-4
High conductivity of dense tetragonal Li7La3Zr2O12
journal, June 2012
- Wolfenstine, Jeff; Rangasamy, Ezhiyl; Allen, Jan L.
- Journal of Power Sources, Vol. 208, p. 193-196
Structural limitations for optimizing garnet-type solid electrolytes: a perspective
journal, January 2014
- Zeier, Wolfgang G.
- Dalton Trans., Vol. 43, Issue 43
Synthesis, ionic conductivity, and chemical compatibility of garnet-like lithium ionic conductor Li5La3Bi2O12
journal, October 2010
- Gao, Y. X.; Wang, X. P.; Wang, W. G.
- Solid State Ionics, Vol. 181, Issue 31-32
The Fabrication of Garnet-Type Li7La3Zr2O12 Solid Electrolyte Materials
journal, April 2016
- Zhang, X.; Fergus, J. W.
- ECS Transactions, Vol. 72, Issue 7
Crystal Structure of Fast Lithium-ion-conducting Cubic Li 7 La 3 Zr 2 O 12
journal, January 2011
- Awaka, Junji; Takashima, Akira; Kataoka, Kunimitsu
- Chemistry Letters, Vol. 40, Issue 1
Nitrogen-free sol–gel synthesis of Al-substituted cubic garnet Li7La3Zr2O12 (LLZO)
journal, March 2015
- Rosenkiewitz, N.; Schuhmacher, J.; Bockmeyer, M.
- Journal of Power Sources, Vol. 278
High lithium ionic conductivity in the garnet-type oxide Li7−XLa3(Zr2−X, NbX)O12 (X=0–2)
journal, March 2011
- Ohta, Shingo; Kobayashi, Tetsuro; Asaoka, Takahiko
- Journal of Power Sources, Vol. 196, Issue 6, p. 3342-3345
Effect of substitution (Ta, Al, Ga) on the conductivity of Li7La3Zr2O12
journal, May 2012
- Allen, J. L.; Wolfenstine, J.; Rangasamy, E.
- Journal of Power Sources, Vol. 206, p. 315-319
Ion transport and phase transition in Li 7−x La 3 (Zr 2−x M x )O 12 (M = Ta 5+ , Nb 5+ , x = 0, 0.25)
journal, January 2012
- Adams, Stefan; Rao, Rayavarapu Prasada
- J. Mater. Chem., Vol. 22, Issue 4
Some Observations on Rechargeable Lithium Electrodes in a Propylene Carbonate Electrolyte
journal, January 1974
- Selim, R.; Bro, P.
- Journal of The Electrochemical Society, Vol. 121, Issue 11
High lithium ionic conductivity in the garnet-type oxide Li 7−2 x La 3 Zr 2− x Mo x O 12 ( x =0-0.3) ceramics by sol-gel method
journal, February 2017
- Liu, Xiaoting; Li, Yuan; Yang, Tiantian
- Journal of the American Ceramic Society, Vol. 100, Issue 4
Inorganic solid Li ion conductors: An overview
journal, June 2009
- Knauth, Philippe
- Solid State Ionics, Vol. 180, Issue 14-16, p. 911-916
Li6ALa2Nb2O12 (A=Ca, Sr, Ba): A New Class of Fast Lithium Ion Conductors with Garnet-Like Structure
journal, February 2005
- Thangadurai, Venkataraman; Weppner, Werner
- Journal of the American Ceramic Society, Vol. 88, Issue 2
Preparation of Li7La3Zr2O12 solid electrolyte via a sol–gel method
journal, April 2014
- Kotobuki, Masashi; Koishi, Masaki
- Ceramics International, Vol. 40, Issue 3
Structure and Li+ dynamics of Sb-doped Li7La3Zr2O12 fast lithium ion conductors
journal, January 2013
- Ramakumar, S.; Satyanarayana, L.; Manorama, Sunkara V.
- Physical Chemistry Chemical Physics, Vol. 15, Issue 27
Characterization of Thin-Film Rechargeable Lithium Batteries with Lithium Cobalt Oxide Cathodes
journal, January 1996
- Wang, B.
- Journal of The Electrochemical Society, Vol. 143, Issue 10
Structure and ionic conductivity in lithium garnets
journal, January 2010
- Cussen, Edmund J.
- Journal of Materials Chemistry, Vol. 20, Issue 25
First-Principles Studies on Cation Dopants and Electrolyte|Cathode Interphases for Lithium Garnets
journal, May 2015
- Miara, Lincoln J.; Richards, William Davidson; Wang, Yan E.
- Chemistry of Materials, Vol. 27, Issue 11
Structure and lithium ion conductivity of bismuth containing lithium garnets Li5La3Bi2O12 and Li6SrLa2Bi2O12
journal, October 2007
- Murugan, Ramaswamy; Weppner, Werner; Schmid-Beurmann, Peter
- Materials Science and Engineering: B, Vol. 143, Issue 1-3
Promises, Challenges, and Recent Progress of Inorganic Solid-State Electrolytes for All-Solid-State Lithium Batteries
journal, February 2018
- Gao, Zhonghui; Sun, Huabin; Fu, Lin
- Advanced Materials, Vol. 30, Issue 17
Gd-doped Li7La3Zr2O12 garnet-type solid electrolytes for all-solid-state Li-Ion batteries
journal, April 2018
- Song, Shidong; Chen, Butian; Ruan, Yanli
- Electrochimica Acta, Vol. 270
Effect of Rb and Ta Doping on the Ionic Conductivity and Stability of the Garnet Li 7+2 x – y (La 3– x Rb x )(Zr 2– y Ta y )O 12 (0 ≤ x ≤ 0.375, 0 ≤ y ≤ 1) Superionic Conductor: A First Principles Investigation
journal, July 2013
- Miara, Lincoln J.; Ong, Shyue Ping; Mo, Yifei
- Chemistry of Materials, Vol. 25, Issue 15
Influence of lithium concentration on the structure and Li + transport properties of cubic phase lithium garnets
journal, January 2015
- Ramakumar, S.; Janani, N.; Murugan, Ramaswamy
- Dalton Transactions, Vol. 44, Issue 2
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
Synthesis and structure analysis of tetragonal Li7La3Zr2O12 with the garnet-related type structure
journal, August 2009
- Awaka, Junji; Kijima, Norihito; Hayakawa, Hiroshi
- Journal of Solid State Chemistry, Vol. 182, Issue 8, p. 2046-2052
Phase stability of a garnet-type lithium ion conductor Li 7 La 3 Zr 2 O 12
journal, January 2014
- Matsui, M.; Takahashi, K.; Sakamoto, K.
- Dalton Trans., Vol. 43, Issue 3
Dramatic reduction in the densification temperature of garnet-type solid electrolytes
journal, February 2018
- Wang, Michael; Sakamoto, Jeff
- Ionics, Vol. 24, Issue 7
Li + transport properties of W substituted Li 7 La 3 Zr 2 O 12 cubic lithium garnets
journal, August 2013
- Dhivya, L.; Janani, N.; Palanivel, B.
- AIP Advances, Vol. 3, Issue 8
Effect of Simultaneous Substitution of Y and Ta on the Stabilization of Cubic Phase, Microstructure, and Li + Conductivity of Li 7 La 3 Zr 2 O 12 Lithium Garnet
journal, October 2014
- Dhivya, L.; Murugan, Ramaswamy
- ACS Applied Materials & Interfaces, Vol. 6, Issue 20
Preparation and enhancement of ionic conductivity in Al-added garnet-like Li6.8La3Zr1.8Bi0.2O12 lithium ionic electrolyte
journal, September 2015
- Xia, Yu; Ma, Liang; Lu, Hui
- Frontiers of Materials Science, Vol. 9, Issue 4
Phase Transformation Kinetics in the System Bismuth Oxide-Zirconia
journal, May 1990
- Takamori, Takeshi; Shafer, Merrill W.
- Journal of the American Ceramic Society, Vol. 73, Issue 5
Structure and dynamics of the fast lithium ion conductor “Li7La3Zr2O12”
journal, January 2011
- Buschmann, Henrik; Dölle, Janis; Berendts, Stefan
- Physical Chemistry Chemical Physics, Vol. 13, Issue 43
Lithium battery chemistries enabled by solid-state electrolytes
journal, February 2017
- Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei
- Nature Reviews Materials, Vol. 2, Issue 4
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
Gallium-Doped Li 7 La 3 Zr 2 O 12 Garnet-Type Electrolytes with High Lithium-Ion Conductivity
journal, January 2017
- Wu, Jian-Fang; Chen, En-Yi; Yu, Yao
- ACS Applied Materials & Interfaces, Vol. 9, Issue 2
Al-doped Li7La3Zr2O12 synthesized by a polymerized complex method
journal, October 2011
- Jin, Ying; McGinn, Paul J.
- Journal of Power Sources, Vol. 196, Issue 20, p. 8683-8687
Crystal Chemistry and Stability of “Li7La3Zr2O12 ” Garnet: A Fast Lithium-Ion Conductor
journal, February 2011
- Geiger, Charles A.; Alekseev, Evgeny; Lazic, Biljana
- Inorganic Chemistry, Vol. 50, Issue 3, p. 1089-1097