Impact of air exposure and surface chemistry on Li-Li7La3Zr2O12 interfacial resistance
Abstract
Li7La3Zr2O12 (LLZO) is a promising solid-state electrolyte that could enable solid-state-batteries (SSB) employing metallic Li anodes. For a SSB to be viable, the stability and charge transfer kinetics at the Li–LLZO interface should foster facile plating and stripping of Li. Contrary to these goals, recent studies have reported high Li–LLZO interfacial resistance which was attributed to a contamination layer that forms upon exposure of LLZO to air. This study clarifies the mechanisms and consequences associated with air exposure of LLZO; additionally, strategies to minimize these effects are described. First-principles calculations reveal that LLZO readily reacts with humid air; the most favorable reaction pathway involves protonation of LLZO and formation of Li2CO3. X-ray photoelectron spectroscopy, scanning electron microscopy, Raman spectroscopy, and transmission electron microscopy were used to characterize the surface and subsurface chemistry of LLZO as a function of relative humidity and exposure time. Additionally, electrochemical impedance spectroscopy was used to measure the Li–LLZO interfacial resistance as a function of surface contamination. These data indicate that air exposure-induced contamination impacts the interfacial resistance significantly, when exposure time exceeds 24 h. The results of this study provide valuable insight into the sensitivity of LLZO to air and how the effects of airmore »
- Authors:
-
[1];
[1];
[2];
[1];
- Univ. of Michigan, Ann Arbor, MI (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1394429
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Materials Chemistry. A
- Additional Journal Information:
- Journal Volume: 5; Journal Issue: 26; Journal ID: ISSN 2050-7488
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE
Citation Formats
Sharafi, Asma, Yu, Seungho, Naguib, Michael, Lee, Marcus, Ma, Cheng, Meyer, Harry M., Nanda, Jagjit, Chi, Maiofang, Siegel, Donald J., and Sakamoto, Jeff. Impact of air exposure and surface chemistry on Li-Li7La3Zr2O12 interfacial resistance. United States: N. p., 2017.
Web. doi:10.1039/C7TA03162A.
Sharafi, Asma, Yu, Seungho, Naguib, Michael, Lee, Marcus, Ma, Cheng, Meyer, Harry M., Nanda, Jagjit, Chi, Maiofang, Siegel, Donald J., & Sakamoto, Jeff. Impact of air exposure and surface chemistry on Li-Li7La3Zr2O12 interfacial resistance. United States. https://doi.org/10.1039/C7TA03162A
Sharafi, Asma, Yu, Seungho, Naguib, Michael, Lee, Marcus, Ma, Cheng, Meyer, Harry M., Nanda, Jagjit, Chi, Maiofang, Siegel, Donald J., and Sakamoto, Jeff. Thu .
"Impact of air exposure and surface chemistry on Li-Li7La3Zr2O12 interfacial resistance". United States. https://doi.org/10.1039/C7TA03162A. https://www.osti.gov/servlets/purl/1394429.
@article{osti_1394429,
title = {Impact of air exposure and surface chemistry on Li-Li7La3Zr2O12 interfacial resistance},
author = {Sharafi, Asma and Yu, Seungho and Naguib, Michael and Lee, Marcus and Ma, Cheng and Meyer, Harry M. and Nanda, Jagjit and Chi, Maiofang and Siegel, Donald J. and Sakamoto, Jeff},
abstractNote = {Li7La3Zr2O12 (LLZO) is a promising solid-state electrolyte that could enable solid-state-batteries (SSB) employing metallic Li anodes. For a SSB to be viable, the stability and charge transfer kinetics at the Li–LLZO interface should foster facile plating and stripping of Li. Contrary to these goals, recent studies have reported high Li–LLZO interfacial resistance which was attributed to a contamination layer that forms upon exposure of LLZO to air. This study clarifies the mechanisms and consequences associated with air exposure of LLZO; additionally, strategies to minimize these effects are described. First-principles calculations reveal that LLZO readily reacts with humid air; the most favorable reaction pathway involves protonation of LLZO and formation of Li2CO3. X-ray photoelectron spectroscopy, scanning electron microscopy, Raman spectroscopy, and transmission electron microscopy were used to characterize the surface and subsurface chemistry of LLZO as a function of relative humidity and exposure time. Additionally, electrochemical impedance spectroscopy was used to measure the Li–LLZO interfacial resistance as a function of surface contamination. These data indicate that air exposure-induced contamination impacts the interfacial resistance significantly, when exposure time exceeds 24 h. The results of this study provide valuable insight into the sensitivity of LLZO to air and how the effects of air contamination can be reversed.},
doi = {10.1039/C7TA03162A},
journal = {Journal of Materials Chemistry. A},
number = 26,
volume = 5,
place = {United States},
year = {Thu Jun 15 00:00:00 EDT 2017},
month = {Thu Jun 15 00:00:00 EDT 2017}
}
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Works referenced in this record:
The rechargeable revolution: A better battery
journal, March 2014
- Van Noorden, Richard
- Nature, Vol. 507, Issue 7490
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
Electrochemical Window of the Li-Ion Solid Electrolyte Li 7 La 3 Zr 2 O 12
journal, January 2017
- Thompson, Travis; Yu, Seungho; Williams, Logan
- ACS Energy Letters, Vol. 2, Issue 2
The Impact of Elastic Deformation on Deposition Kinetics at Lithium/Polymer Interfaces
journal, January 2005
- Monroe, Charles; Newman, John
- Journal of The Electrochemical Society, Vol. 152, Issue 2
Understanding Solid Electrolyte Interface Film Formation on Graphite Electrodes
journal, January 2001
- Zhang, Shengshui; Ding, Michael S.; Xu, Kang
- Electrochemical and Solid-State Letters, Vol. 4, Issue 12
Aging Mechanisms of LiFePO[sub 4] Batteries Deduced by Electrochemical and Structural Analyses
journal, January 2010
- Liu, Ping; Wang, John; Hicks-Garner, Jocelyn
- Journal of The Electrochemical Society, Vol. 157, Issue 4
Review of selected electrode–solution interactions which determine the performance of Li and Li ion batteries
journal, August 2000
- Aurbach, Doron
- Journal of Power Sources, Vol. 89, Issue 2
Main aging mechanisms in Li ion batteries
journal, August 2005
- Broussely, M.; Biensan, Ph.; Bonhomme, F.
- Journal of Power Sources, Vol. 146, Issue 1-2
Electrochemical impedance study on the low temperature of Li-ion batteries
journal, March 2004
- Zhang, S. S.; Xu, K.; Jow, T. R.
- Electrochimica Acta, Vol. 49, Issue 7
The origin of high electrolyte–electrode interfacial resistances in lithium cells containing garnet type solid electrolytes
journal, January 2014
- Cheng, Lei; Crumlin, Ethan J.; Chen, Wei
- Phys. Chem. Chem. Phys., Vol. 16, Issue 34
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
Instability of Lithium Garnets against Moisture. Structural Characterization and Dynamics of Li 7- x H x La 3 Sn 2 O 12 and Li 5- x H x La 3 Nb 2 O 12
journal, August 2012
- Galven, Cyrille; Dittmer, Jens; Suard, Emmanuelle
- Chemistry of Materials, Vol. 24, Issue 17
Low temperature cubic garnet-type CO2-doped Li7La3Zr2O12
journal, February 2013
- Toda, S.; Ishiguro, K.; Shimonishi, Y.
- Solid State Ionics, Vol. 233
Ionic Conductivity and Air Stability of Al-Doped Li 7 La 3 Zr 2 O 12 Sintered in Alumina and Pt Crucibles
journal, February 2016
- Xia, Wenhao; Xu, Biyi; Duan, Huanan
- ACS Applied Materials & Interfaces, Vol. 8, Issue 8
Li7La3Zr2O12 electrolyte stability in air and fabrication of a Li/Li7La3Zr2O12/Cu0.1V2O5 solid-state battery
journal, October 2013
- Jin, Ying; McGinn, Paul J.
- Journal of Power Sources, Vol. 239
Soft-Chemistry of Garnet-Type Li 5+ x Ba x La 3– x Nb 2 O 12 ( x = 0, 0.5, 1): Reversible H + ↔ Li + Ion-Exchange Reaction and Their X-ray, 7 Li MAS NMR, IR, and AC Impedance Spectroscopy Characterization
journal, September 2011
- Truong, Lina; Thangadurai, Venkataraman
- Chemistry of Materials, Vol. 23, Issue 17
First Total H + /Li + Ion Exchange in Garnet-Type Li 5 La 3 Nb 2 O 12 Using Organic Acids and Studies on the Effect of Li Stuffing
journal, January 2012
- Truong, Lina; Thangadurai, Venkataraman
- Inorganic Chemistry, Vol. 51, Issue 3
Cubic phases of garnet-type Li7La3Zr2O12: the role of hydration
journal, January 2013
- Larraz, G.; Orera, A.; Sanjuán, M. L.
- Journal of Materials Chemistry A, Vol. 1, Issue 37
Interrelationships among Grain Size, Surface Composition, Air Stability, and Interfacial Resistance of Al-Substituted Li 7 La 3 Zr 2 O 12 Solid Electrolytes
journal, August 2015
- Cheng, Lei; Wu, Cheng Hao; Jarry, Angelique
- ACS Applied Materials & Interfaces, Vol. 7, Issue 32
Effect of Li+/H+ exchange in water treated Ta-doped Li7La3Zr2O12
journal, September 2016
- Yow, Zhen Feng; Oh, Yuan Liang; Gu, Wenyi
- Solid State Ionics, Vol. 292
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Elastic Properties of the Solid Electrolyte Li 7 La 3 Zr 2 O 12 (LLZO)
journal, December 2015
- Yu, Seungho; Schmidt, Robert D.; Garcia-Mendez, Regina
- Chemistry of Materials, Vol. 28, Issue 1
Excellent Stability of a Lithium-Ion-Conducting Solid Electrolyte upon Reversible Li + /H + Exchange in Aqueous Solutions
journal, October 2014
- Ma, Cheng; Rangasamy, Ezhiylmurugan; Liang, Chengdu
- Angewandte Chemie, Vol. 127, Issue 1
NMR study of Li distribution in Li 7−x H x La 3 Zr 2 O 12 garnets
journal, January 2015
- Larraz, G.; Orera, A.; Sanz, J.
- Journal of Materials Chemistry A, Vol. 3, Issue 10
Special points for Brillouin-zone integrations
journal, June 1976
- Monkhorst, Hendrik J.; Pack, James D.
- Physical Review B, Vol. 13, Issue 12, p. 5188-5192
The Compressibility of Media under Extreme Pressures
journal, September 1944
- Murnaghan, F. D.
- Proceedings of the National Academy of Sciences, Vol. 30, Issue 9
Thermodynamic Properties of Key Organic Oxygen Compounds in the Carbon Range C 1 to C 4 . Part 1. Properties of Condensed Phases
journal, January 1985
- Wilhoit, Randolph C.; Chao, Jing; Hall, Kenneth R.
- Journal of Physical and Chemical Reference Data, Vol. 14, Issue 1
Reaction mechanisms of Li0.30La0.57TiO3 powder with ambient air: H+/Li+ exchange with water and Li2CO3 formation
journal, January 2010
- Boulant, Anthony; Bardeau, Jean Francois; Jouanneaux, Alain
- Dalton Transactions, Vol. 39, Issue 16
Tetragonal vs. cubic phase stability in Al – free Ta doped Li 7 La 3 Zr 2 O 12 (LLZO)
journal, January 2014
- Thompson, Travis; Wolfenstine, Jeff; Allen, Jan L.
- J. Mater. Chem. A, Vol. 2, Issue 33
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
Synthesis and Raman micro-spectroscopy investigation of Li7La3Zr2O12
journal, January 2013
- Tietz, F.; Wegener, T.; Gerhards, M. T.
- Solid State Ionics, Vol. 230
Lithium K-edge XANES spectra for lithium compounds
journal, January 2002
- Tsuji, Junichi; Nakamatsu, Hirohide; Mukoyama, Takeshi
- X-Ray Spectrometry, Vol. 31, Issue 4
Electroceramics: Characterization by Impedance Spectroscopy
journal, March 1990
- Irvine, John T. S.; Sinclair, Derek C.; West, Anthony R.
- Advanced Materials, Vol. 2, Issue 3
A Tale of Two Sites: On Defining the Carrier Concentration in Garnet-Based Ionic Conductors for Advanced Li Batteries
journal, March 2015
- Thompson, Travis; Sharafi, Asma; Johannes, Michelle D.
- Advanced Energy Materials, Vol. 5, Issue 11
Characterizing the Li–Li7La3Zr2O12 interface stability and kinetics as a function of temperature and current density
journal, January 2016
- Sharafi, Asma; Meyer, Harry M.; Nanda, Jagjit
- Journal of Power Sources, Vol. 302
Electrochemical performance of an all-solid-state lithium ion battery with garnet-type oxide electrolyte
journal, March 2012
- Ohta, Shingo; Kobayashi, Tetsuro; Seki, Juntaro
- Journal of Power Sources, Vol. 202
Electrochemical Stability of Li6.5La3Zr1.5M0.5O12 (M = Nb or Ta) against Metallic Lithium
journal, May 2016
- Kim, Yunsung; Yoo, Aeri; Schmidt, Robert
- Frontiers in Energy Research, Vol. 4
Excellent Stability of a Lithium-Ion-Conducting Solid Electrolyte upon Reversible Li + /H + Exchange in Aqueous Solutions
journal, October 2014
- Ma, Cheng; Rangasamy, Ezhiylmurugan; Liang, Chengdu
- Angewandte Chemie International Edition, Vol. 54, Issue 1
Fast Lithium Ion Conduction in Garnet-Type Li7La3Zr2O12.
journal, December 2007
- Murugan, Ramaswamy; Thangadurai, Venkataraman; Weppner, Werner
- ChemInform, Vol. 38, Issue 50
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021
- Chen, Ruyi; Cui, Qirui; Liao, Liyang
- Nature Communications, Vol. 12, Issue 1
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect
journal, February 2020
- Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna
- Scientific Reports, Vol. 10, Issue 1
Works referencing / citing this record:
The Ab Initio Calculations on the Areal Specific Resistance of Li‐Metal/Li 7 La 3 Zr 2 O 12 Interphase
journal, April 2019
- Gao, Jian; Guo, Xuyun; Li, Yutao
- Advanced Theory and Simulations
Dopant‐Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal
journal, January 2019
- Zhu, Yisi; Connell, Justin G.; Tepavcevic, Sanja
- Advanced Energy Materials, Vol. 9, Issue 12
Interface-Engineered Li 7 La 3 Zr 2 O 12 -Based Garnet Solid Electrolytes with Suppressed Li-Dendrite Formation and Enhanced Electrochemical Performance
journal, October 2018
- Zhang, Zhaoshuai; Zhang, Long; Liu, Yanyan
- ChemSusChem, Vol. 11, Issue 21
In situ X-ray photoelectron spectroscopy investigation of the solid electrolyte interphase in a Li/Li6.4Ga0.2La3Zr2O12/LiFePO4 all-solid-state battery
journal, June 2019
- Liu, Zhen; Li, Guozhu; Borodin, Andriy
- Journal of Solid State Electrochemistry, Vol. 23, Issue 7
Hybrid electrolyte with robust garnet-ceramic electrolyte for lithium anode protection in lithium-oxygen batteries
journal, May 2018
- Wang, Jin; Yin, Yanbin; Liu, Tong
- Nano Research, Vol. 11, Issue 6
Fundamentals of inorganic solid-state electrolytes for batteries
journal, August 2019
- Famprikis, Theodosios; Canepa, Pieremanuele; Dawson, James A.
- Nature Materials, Vol. 18, Issue 12
Understanding interface stability in solid-state batteries
journal, December 2019
- Xiao, Yihan; Wang, Yan; Bo, Shou-Hang
- Nature Reviews Materials, Vol. 5, Issue 2
On the interfacial charge transfer between solid and liquid Li + electrolytes
journal, January 2017
- Schleutker, Marco; Bahner, Jochen; Tsai, Chih-Long
- Phys. Chem. Chem. Phys., Vol. 19, Issue 39
Elucidating the role of dopants in the critical current density for dendrite formation in garnet electrolytes
journal, January 2018
- Pesci, Federico M.; Brugge, Rowena H.; Hekselman, A. K. Ola
- Journal of Materials Chemistry A, Vol. 6, Issue 40
Atomic layer deposition and first principles modeling of glassy Li 3 BO 3 –Li 2 CO 3 electrolytes for solid-state Li metal batteries
journal, January 2018
- Kazyak, Eric; Chen, Kuan-Hung; Davis, Andrew L.
- Journal of Materials Chemistry A, Vol. 6, Issue 40
Local Li-ion conductivity changes within Al stabilized Li 7 La 3 Zr 2 O 12 and their relationship to three-dimensional variations of the bulk composition
journal, January 2019
- Smetaczek, Stefan; Wachter-Welzl, Andreas; Wagner, Reinhard
- Journal of Materials Chemistry A, Vol. 7, Issue 12
The conduction process of grain and grain boundary in the semiconductive zirconium oxynitride thin film
journal, July 2019
- Lin, Zude; Zhan, Guanghui; Li, Xiuyan
- Semiconductor Science and Technology, Vol. 34, Issue 8
Electrochemical Stability of Garnet-Type Li 7 La 2.75 Ca 0.25 Zr 1.75 Nb 0.25 O 12 with and without Atomic Layer Deposited-Al 2 O 3 under CO 2 and Humidity
journal, January 2019
- Hofstetter, Kyle; Samson, Alfred Junio; Dai, Jiaqi
- Journal of The Electrochemical Society, Vol. 166, Issue 10