Dopant-Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal
Abstract
Li7La3Zr2O12 (LLZO) garnet-based materials doped with Al, Nb or Ta to stabilize the Li+-conductive cubic phase are a particularly promising class of solid electrolytes for all-solid-state lithium metal batteries. Understanding of the intrinsic reactivity between solid electrolytes and relevant electrode materials is crucial to developing high voltage solid-state batteries with long lifetimes. Using a novel, surface science-based approach to characterize the intrinsic reactivity of the Li-solid electrolyte interface, we determine that, surprisingly, some degree of Zr reduction takes place for all three dopant types, with the extent of reduction increasing as Ta < Nb < Al. Significant reduction of Nb also takes place for Nb-doped LLZO, with electrochemical impedance spectroscopy (EIS) of Li||Nb-LLZO||Li symmetric cells further revealing significant increases in impedance with time and suggesting that the Nb reduction propagates into the bulk. Density functional theory (DFT) calculations reveal that Nb-doped material shows a strong preference for Nb dopants towards the interface between LLZO and Li, while Ta does not exhibit a similar preference. Furthermore EIS and DFT results, coupled with the observed reduction of Zr at the interface, are consistent with the formation of an “oxygen-deficient interphase” (ODI) layer whose structure determines the stability of the LLZO-Li interface.
- Authors:
-
[1];
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Univ. of Michigan, Ann Arbor, MI (United States)
- Argonne National Lab. (ANL), Lemont, IL (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V). Battery Materials Research (BMR) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; USDOE
- OSTI Identifier:
- 1508374
- Alternate Identifier(s):
- OSTI ID: 1494204
- Grant/Contract Number:
- AC02-06CH11357; AC02‐06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Energy Materials
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 12; Journal ID: ISSN 1614-6832
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Li metal; buried interface; solid electrolytes; solid‐state batteries; surface science
Citation Formats
Zhu, Yisi, Connell, Justin G., Tepavcevic, Sanja, Zapol, Peter, Garcia‐Mendez, Regina, Taylor, Nathan J., Sakamoto, Jeff, Ingram, Brian J., Curtiss, Larry A., Freeland, John W., Fong, Dillon D., and Markovic, Nenad M.. Dopant-Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal. United States: N. p., 2019.
Web. doi:10.1002/aenm.201803440.
Zhu, Yisi, Connell, Justin G., Tepavcevic, Sanja, Zapol, Peter, Garcia‐Mendez, Regina, Taylor, Nathan J., Sakamoto, Jeff, Ingram, Brian J., Curtiss, Larry A., Freeland, John W., Fong, Dillon D., & Markovic, Nenad M.. Dopant-Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal. United States. https://doi.org/10.1002/aenm.201803440
Zhu, Yisi, Connell, Justin G., Tepavcevic, Sanja, Zapol, Peter, Garcia‐Mendez, Regina, Taylor, Nathan J., Sakamoto, Jeff, Ingram, Brian J., Curtiss, Larry A., Freeland, John W., Fong, Dillon D., and Markovic, Nenad M.. Sun .
"Dopant-Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal". United States. https://doi.org/10.1002/aenm.201803440. https://www.osti.gov/servlets/purl/1508374.
@article{osti_1508374,
title = {Dopant-Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal},
author = {Zhu, Yisi and Connell, Justin G. and Tepavcevic, Sanja and Zapol, Peter and Garcia‐Mendez, Regina and Taylor, Nathan J. and Sakamoto, Jeff and Ingram, Brian J. and Curtiss, Larry A. and Freeland, John W. and Fong, Dillon D. and Markovic, Nenad M.},
abstractNote = {Li7La3Zr2O12 (LLZO) garnet-based materials doped with Al, Nb or Ta to stabilize the Li+-conductive cubic phase are a particularly promising class of solid electrolytes for all-solid-state lithium metal batteries. Understanding of the intrinsic reactivity between solid electrolytes and relevant electrode materials is crucial to developing high voltage solid-state batteries with long lifetimes. Using a novel, surface science-based approach to characterize the intrinsic reactivity of the Li-solid electrolyte interface, we determine that, surprisingly, some degree of Zr reduction takes place for all three dopant types, with the extent of reduction increasing as Ta < Nb < Al. Significant reduction of Nb also takes place for Nb-doped LLZO, with electrochemical impedance spectroscopy (EIS) of Li||Nb-LLZO||Li symmetric cells further revealing significant increases in impedance with time and suggesting that the Nb reduction propagates into the bulk. Density functional theory (DFT) calculations reveal that Nb-doped material shows a strong preference for Nb dopants towards the interface between LLZO and Li, while Ta does not exhibit a similar preference. Furthermore EIS and DFT results, coupled with the observed reduction of Zr at the interface, are consistent with the formation of an “oxygen-deficient interphase” (ODI) layer whose structure determines the stability of the LLZO-Li interface.},
doi = {10.1002/aenm.201803440},
journal = {Advanced Energy Materials},
number = 12,
volume = 9,
place = {United States},
year = {2019},
month = {2}
}
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Works referenced in this record:
Negating interfacial impedance in garnet-based solid-state Li metal batteries
journal, December 2016
- Han, Xiaogang; Gong, Yunhui; Fu, Kun (Kelvin)
- Nature Materials, Vol. 16, Issue 5
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
Interface-Engineered All-Solid-State Li-Ion Batteries Based on Garnet-Type Fast Li + Conductors
journal, July 2016
- van den Broek, Jan; Afyon, Semih; Rupp, Jennifer L. M.
- Advanced Energy Materials, Vol. 6, Issue 19
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
New horizons for inorganic solid state ion conductors
journal, January 2018
- Zhang, Zhizhen; Shao, Yuanjun; Lotsch, Bettina
- Energy & Environmental Science, Vol. 11, Issue 8
Stabilization of cubic lithium-stuffed garnets of the type “Li7La3Zr2O12” by addition of gallium
journal, March 2013
- El Shinawi, Hany; Janek, Jürgen
- Journal of Power Sources, Vol. 225
Lithium Distribution in Aluminum-Free Cubic Li 7 La 3 Zr 2 O 12
journal, August 2011
- Xie, Hui; Alonso, Jose A.; Li, Yutao
- Chemistry of Materials, Vol. 23, Issue 16
Structure, Chemistry, and Charge Transfer Resistance of the Interface between Li 7 La 3 Zr 2 O 12 Electrolyte and LiCoO 2 Cathode
journal, July 2018
- Vardar, Gulin; Bowman, William J.; Lu, Qiyang
- Chemistry of Materials, Vol. 30, Issue 18
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
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
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
Conformal, Nanoscale ZnO Surface Modification of Garnet-Based Solid-State Electrolyte for Lithium Metal Anodes
journal, December 2016
- Wang, Chengwei; Gong, Yunhui; Liu, Boyang
- Nano Letters, Vol. 17, Issue 1
The Migration of Metal and Oxygen during Anodic Film Formation
journal, January 1965
- Davies, J. A.; Domeij, B.; Pringle, J. P. S.
- Journal of The Electrochemical Society, Vol. 112, Issue 7
High-power all-solid-state batteries using sulfide superionic conductors
journal, March 2016
- Kato, Yuki; Hori, Satoshi; Saito, Toshiya
- Nature Energy, Vol. 1, Issue 4
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
Protected Lithium-Metal Anodes in Batteries: From Liquid to Solid
journal, July 2017
- Yang, Chunpeng; Fu, Kun; Zhang, Ying
- Advanced Materials, Vol. 29, Issue 36
Crystal Orientation-Dependent Reactivity of Oxide Surfaces in Contact with Lithium Metal
journal, April 2018
- Connell, Justin G.; Zhu, Yisi; Zapol, Peter
- ACS Applied Materials & Interfaces, Vol. 10, Issue 20
Fabrication of all-solid-state lithium battery with lithium metal anode using Al2O3-added Li7La3Zr2O12 solid electrolyte
journal, September 2011
- Kotobuki, Masashi; Kanamura, Kiyoshi; Sato, Yosuke
- Journal of Power Sources, Vol. 196, Issue 18
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Electroceramics: Characterization by Impedance Spectroscopy
journal, March 1990
- Irvine, John T. S.; Sinclair, Derek C.; West, Anthony R.
- Advanced Materials, Vol. 2, Issue 3
First principles study on electrochemical and chemical stability of solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries
journal, January 2016
- Zhu, Yizhou; He, Xingfeng; Mo, Yifei
- Journal of Materials Chemistry A, Vol. 4, Issue 9
Reducing Interfacial Resistance between Garnet-Structured Solid-State Electrolyte and Li-Metal Anode by a Germanium Layer
journal, April 2017
- Luo, Wei; Gong, Yunhui; Zhu, Yizhou
- Advanced Materials, Vol. 29, Issue 22
An in situ element permeation constructed high endurance Li–LLZO interface at high current densities
journal, January 2018
- Lu, Yang; Huang, Xiao; Ruan, Yadong
- Journal of Materials Chemistry A, Vol. 6, Issue 39
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
Electrochemical Stability of Li 10 GeP 2 S 12 and Li 7 La 3 Zr 2 O 12 Solid Electrolytes
journal, January 2016
- Han, Fudong; Zhu, Yizhou; He, Xingfeng
- Advanced Energy Materials, Vol. 6, Issue 8
Effect of microstructure and surface impurity segregation on the electrical and electrochemical properties of dense Al-substituted Li 7 La 3 Zr 2 O 12
journal, January 2014
- Cheng, Lei; Park, Joong Sun; Hou, Huaming
- J. Mater. Chem. A, Vol. 2, Issue 1
Correlating the interface resistance and surface adhesion of the Li metal-solid electrolyte interface
journal, February 2018
- Wang, Michael; Sakamoto, Jeff
- Journal of Power Sources, Vol. 377
Electrochemical Nature of the Cathode Interface for a Solid-State Lithium-Ion Battery: Interface between LiCoO 2 and Garnet-Li 7 La 3 Zr 2 O 12
journal, October 2016
- Park, Kyusung; Yu, Byeong-Chul; Jung, Ji-Won
- Chemistry of Materials, Vol. 28, Issue 21
Chemical stability of cubic Li7La3Zr2O12 with molten lithium at elevated temperature
journal, April 2013
- Wolfenstine, J.; Allen, J. L.; Read, J.
- Journal of Materials Science, Vol. 48, Issue 17
Electrochemical impedance of electrolyte/electrode interfaces of lithium-ion rechargeable batteries
journal, January 2006
- Itagaki, Masayuki; Yotsuda, Sachiko; Kobari, Nao
- Electrochimica Acta, Vol. 51, Issue 8-9
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
Initial stages of oxide formation on the Zr surface at low oxygen pressure: An in situ FIM and XPS study
journal, December 2015
- Bespalov, I.; Datler, M.; Buhr, S.
- Ultramicroscopy, Vol. 159
Garnet Electrolytes for Solid State Batteries: Visualization of Moisture-Induced Chemical Degradation and Revealing Its Impact on the Li-Ion Dynamics
journal, May 2018
- Brugge, Rowena H.; Hekselman, A. K. Ola; Cavallaro, Andrea
- Chemistry of Materials, Vol. 30, Issue 11
A solid future for battery development
journal, September 2016
- Janek, Jürgen; Zeier, Wolfgang G.
- Nature Energy, Vol. 1, Issue 9
The role of the solid electrolyte interphase layer in preventing Li dendrite growth in solid-state batteries
journal, January 2018
- Wu, Bingbin; Wang, Shanyu; Lochala, Joshua
- Energy & Environmental Science, Vol. 11, Issue 7
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
Interfacial Stability of Li Metal–Solid Electrolyte Elucidated via in Situ Electron Microscopy
journal, October 2016
- Ma, Cheng; Cheng, Yongqiang; Yin, Kuibo
- Nano Letters, Vol. 16, Issue 11
Impact of air exposure and surface chemistry on Li–Li 7 La 3 Zr 2 O 12 interfacial resistance
journal, January 2017
- Sharafi, Asma; Yu, Seungho; Naguib, Michael
- Journal of Materials Chemistry A, Vol. 5, Issue 26
On the determination of atomic charge via ESCA including application to organometallics
journal, February 1996
- Sleigh, Christopher; Pijpers, A. P.; Jaspers, Alex
- Journal of Electron Spectroscopy and Related Phenomena, Vol. 77, Issue 1
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
Resolving the Grain Boundary and Lattice Impedance of Hot-Pressed Li 7 La 3 Zr 2 O 12 Garnet Electrolytes
journal, July 2013
- Tenhaeff, Wyatt E.; Rangasamy, Ezhiyl; Wang, Yangyang
- ChemElectroChem, Vol. 1, Issue 2
Surface Chemistry Mechanism of Ultra-Low Interfacial Resistance in the Solid-State Electrolyte Li 7 La 3 Zr 2 O 12
journal, September 2017
- Sharafi, Asma; Kazyak, Eric; Davis, Andrew L.
- Chemistry of Materials, Vol. 29, Issue 18
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
Effect of Pore Connectivity on Li Dendrite Propagation within LLZO Electrolytes Observed with Synchrotron X-ray Tomography
journal, March 2018
- Shen, Fengyu; Dixit, Marm B.; Xiao, Xianghui
- ACS Energy Letters, Vol. 3, Issue 4
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
Lithium battery chemistries enabled by solid-state electrolytes
journal, February 2017
- Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei
- Nature Reviews Materials, Vol. 2, Issue 4
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 Electronic Conductivity of Single Crystalline Ga‐Stabilized Cubic Li 7 La 3 Zr 2 O 12 : A Technologically Relevant Parameter for All‐Solid‐State Batteries
journal, June 2020
- Philipp, Martin; Gadermaier, Bernhard; Posch, Patrick
- Advanced Materials Interfaces
Inside or Outside: Origin of Lithium Dendrite Formation of All Solid‐State Electrolytes
journal, September 2019
- Mo, Fangjie; Ruan, Jiafeng; Sun, Shuxian
- Advanced Energy Materials, Vol. 9, Issue 40
Diffusion Limitation of Lithium Metal and Li–Mg Alloy Anodes on LLZO Type Solid Electrolytes as a Function of Temperature and Pressure
journal, October 2019
- Krauskopf, Thorben; Mogwitz, Boris; Rosenbach, Carolin
- Advanced Energy Materials, Vol. 9, Issue 44
A Lithium Oxythioborosilicate Solid Electrolyte Glass with Superionic Conductivity
journal, January 2020
- Kaup, Kavish; Bazak, J. David; Vajargah, Shahrzad Hosseini
- Advanced Energy Materials, Vol. 10, Issue 8
Air‐Stable and Dendrite‐Free Lithium Metal Anodes Enabled by a Hybrid Interphase of C 60 and Mg
journal, December 2019
- Xu, Qingshuai; Lin, Jiajin; Ye, Changchun
- Advanced Energy Materials, Vol. 10, Issue 6
Li/Garnet Interface Stabilization by Thermal‐Decomposition Vapor Deposition of an Amorphous Carbon Layer
journal, March 2020
- Feng, Wuliang; Dong, Xiaoli; Zhang, Xiang
- Angewandte Chemie International Edition, Vol. 59, Issue 13
Virus‐Templated Nickel Phosphide Nanofoams as Additive‐Free, Thin‐Film Li‐Ion Microbattery Anodes
journal, September 2019
- Records, William C.; Wei, Shuya; Belcher, Angela M.
- Small, Vol. 15, Issue 44
Design Principles of the Anode–Electrolyte Interface for All Solid‐State Lithium Metal Batteries
journal, October 2019
- Shen, Zeyu; Zhang, Weidong; Zhu, Guannan
- Small Methods, Vol. 4, Issue 1
Microstrain and electrochemical performance of garnet solid electrolyte integrated in a hybrid battery cell
journal, January 2019
- Botros, Miriam; Scherer, Torsten; Popescu, Radian
- RSC Advances, Vol. 9, Issue 53
Rationalizing the interphase stability of Li|doped-Li 7 La 3 Zr 2 O 12 via automated reaction screening and machine learning
journal, January 2019
- Liu, Bo; Yang, Jiong; Yang, Hongliang
- Journal of Materials Chemistry A, Vol. 7, Issue 34
Li/Garnet Interface Stabilization by Thermal‐Decomposition Vapor Deposition of an Amorphous Carbon Layer
journal, February 2020
- Feng, Wuliang; Dong, Xiaoli; Zhang, Xiang
- Angewandte Chemie, Vol. 132, Issue 13
Microstrain and electrochemical performance of garnet solid electrolyte integrated in a hybrid battery cell
text, January 2019
- Botros, M.; Scherer, T.; Popescu, R.
- Karlsruhe