Dopant-Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal

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.

doi:10.1002/aenm.201803440

Title: Dopant-Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal

Journal Article · 10 February 2019 · Advanced Energy Materials

DOI: https://doi.org/10.1002/aenm.201803440 · OSTI ID:1508374

Zhu, Yisi ^[1];

^[1]; Tepavcevic, Sanja ^[1]; Zapol, Peter ^[1]; Garcia‐Mendez, Regina ^[2]; Taylor, Nathan J. ^[2]; Sakamoto, Jeff ^[2]; Ingram, Brian J. ^[3]; Curtiss, Larry A. ^[1]; Freeland, John W. ^[1]; Fong, Dillon D. ^[3]; Markovic, Nenad M. ^[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)

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.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: 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

Grant/Contract Number:: AC02-06CH11357; AC02‐06CH11357

OSTI ID:: 1508374

Alternate ID(s):: OSTI ID: 1494204

Journal Information:: Advanced Energy Materials, Vol. 9, Issue 12; ISSN 1614-6832

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 179 works

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References (51)

Negating interfacial impedance in garnet-based solid-state Li metal batteries Han, Xiaogang; Gong, Yunhui; Fu, Kun (Kelvin) Nature Materials, Vol. 16, Issue 5 https://doi.org/10.1038/nmat4821	journal	December 2016
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Elastic Properties of the Solid Electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ (LLZO) Yu, Seungho; Schmidt, Robert D.; Garcia-Mendez, Regina Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b03854	journal	December 2015
Interface-Engineered All-Solid-State Li-Ion Batteries Based on Garnet-Type Fast Li ⁺ Conductors van den Broek, Jan; Afyon, Semih; Rupp, Jennifer L. M. Advanced Energy Materials, Vol. 6, Issue 19 https://doi.org/10.1002/aenm.201600736	journal	July 2016
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
New horizons for inorganic solid state ion conductors Zhang, Zhizhen; Shao, Yuanjun; Lotsch, Bettina Energy & Environmental Science, Vol. 11, Issue 8 https://doi.org/10.1039/C8EE01053F	journal	January 2018
Stabilization of cubic lithium-stuffed garnets of the type “Li7La3Zr2O12” by addition of gallium El Shinawi, Hany; Janek, Jürgen Journal of Power Sources, Vol. 225 https://doi.org/10.1016/j.jpowsour.2012.09.111	journal	March 2013
Lithium Distribution in Aluminum-Free Cubic Li ₇ La ₃ Zr ₂ O ₁₂ Xie, Hui; Alonso, Jose A.; Li, Yutao Chemistry of Materials, Vol. 23, Issue 16 https://doi.org/10.1021/cm201671k	journal	August 2011
Structure, Chemistry, and Charge Transfer Resistance of the Interface between Li ₇ La ₃ Zr ₂ O ₁₂ Electrolyte and LiCoO ₂ Cathode Vardar, Gulin; Bowman, William J.; Lu, Qiyang Chemistry of Materials, Vol. 30, Issue 18 https://doi.org/10.1021/acs.chemmater.8b01713	journal	July 2018
A Tale of Two Sites: On Defining the Carrier Concentration in Garnet-Based Ionic Conductors for Advanced Li Batteries Thompson, Travis; Sharafi, Asma; Johannes, Michelle D. Advanced Energy Materials, Vol. 5, Issue 11 https://doi.org/10.1002/aenm.201500096	journal	March 2015
Characterizing the Li–Li7La3Zr2O12 interface stability and kinetics as a function of temperature and current density Sharafi, Asma; Meyer, Harry M.; Nanda, Jagjit Journal of Power Sources, Vol. 302 https://doi.org/10.1016/j.jpowsour.2015.10.053	journal	January 2016
Effect of substitution (Ta, Al, Ga) on the conductivity of Li₇La₃Zr₂O₁₂ Allen, J. L.; Wolfenstine, J.; Rangasamy, E. Journal of Power Sources, Vol. 206, p. 315-319 https://doi.org/10.1016/j.jpowsour.2012.01.131	journal	May 2012
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Conformal, Nanoscale ZnO Surface Modification of Garnet-Based Solid-State Electrolyte for Lithium Metal Anodes Wang, Chengwei; Gong, Yunhui; Liu, Boyang Nano Letters, Vol. 17, Issue 1 https://doi.org/10.1021/acs.nanolett.6b04695	journal	December 2016
The Migration of Metal and Oxygen during Anodic Film Formation Davies, J. A.; Domeij, B.; Pringle, J. P. S. Journal of The Electrochemical Society, Vol. 112, Issue 7 https://doi.org/10.1149/1.2423662	journal	January 1965
High-power all-solid-state batteries using sulfide superionic conductors Kato, Yuki; Hori, Satoshi; Saito, Toshiya Nature Energy, Vol. 1, Issue 4 https://doi.org/10.1038/nenergy.2016.30	journal	March 2016
First-Principles Studies on Cation Dopants and Electrolyte\|Cathode Interphases for Lithium Garnets Miara, Lincoln J.; Richards, William Davidson; Wang, Yan E. Chemistry of Materials, Vol. 27, Issue 11 https://doi.org/10.1021/acs.chemmater.5b01023	journal	May 2015
Protected Lithium-Metal Anodes in Batteries: From Liquid to Solid Yang, Chunpeng; Fu, Kun; Zhang, Ying Advanced Materials, Vol. 29, Issue 36 https://doi.org/10.1002/adma.201701169	journal	July 2017
Crystal Orientation-Dependent Reactivity of Oxide Surfaces in Contact with Lithium Metal Connell, Justin G.; Zhu, Yisi; Zapol, Peter ACS Applied Materials & Interfaces, Vol. 10, Issue 20 https://doi.org/10.1021/acsami.8b03078	journal	April 2018
Fabrication of all-solid-state lithium battery with lithium metal anode using Al2O3-added Li7La3Zr2O12 solid electrolyte Kotobuki, Masashi; Kanamura, Kiyoshi; Sato, Yosuke Journal of Power Sources, Vol. 196, Issue 18 https://doi.org/10.1016/j.jpowsour.2011.04.047	journal	September 2011
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Electroceramics: Characterization by Impedance Spectroscopy Irvine, John T. S.; Sinclair, Derek C.; West, Anthony R. Advanced Materials, Vol. 2, Issue 3 https://doi.org/10.1002/adma.19900020304	journal	March 1990
First principles study on electrochemical and chemical stability of solid electrolyte–electrode interfaces in all-solid-state Li-ion batteries Zhu, Yizhou; He, Xingfeng; Mo, Yifei Journal of Materials Chemistry A, Vol. 4, Issue 9 https://doi.org/10.1039/C5TA08574H	journal	January 2016
Reducing Interfacial Resistance between Garnet-Structured Solid-State Electrolyte and Li-Metal Anode by a Germanium Layer Luo, Wei; Gong, Yunhui; Zhu, Yizhou Advanced Materials, Vol. 29, Issue 22 https://doi.org/10.1002/adma.201606042	journal	April 2017
An in situ element permeation constructed high endurance Li–LLZO interface at high current densities Lu, Yang; Huang, Xiao; Ruan, Yadong Journal of Materials Chemistry A, Vol. 6, Issue 39 https://doi.org/10.1039/C8TA07241H	journal	January 2018
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 Miara, Lincoln J.; Ong, Shyue Ping; Mo, Yifei Chemistry of Materials, Vol. 25, Issue 15 https://doi.org/10.1021/cm401232r	journal	July 2013
Electrochemical Stability of Li ₁₀ GeP ₂ S ₁₂ and Li ₇ La ₃ Zr ₂ O ₁₂ Solid Electrolytes Han, Fudong; Zhu, Yizhou; He, Xingfeng Advanced Energy Materials, Vol. 6, Issue 8 https://doi.org/10.1002/aenm.201501590	journal	January 2016
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 Cheng, Lei; Park, Joong Sun; Hou, Huaming J. Mater. Chem. A, Vol. 2, Issue 1 https://doi.org/10.1039/C3TA13999A	journal	January 2014
Correlating the interface resistance and surface adhesion of the Li metal-solid electrolyte interface Wang, Michael; Sakamoto, Jeff Journal of Power Sources, Vol. 377 https://doi.org/10.1016/j.jpowsour.2017.11.078	journal	February 2018
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 Park, Kyusung; Yu, Byeong-Chul; Jung, Ji-Won Chemistry of Materials, Vol. 28, Issue 21 https://doi.org/10.1021/acs.chemmater.6b03870	journal	October 2016
Chemical stability of cubic Li7La3Zr2O12 with molten lithium at elevated temperature Wolfenstine, J.; Allen, J. L.; Read, J. Journal of Materials Science, Vol. 48, Issue 17 https://doi.org/10.1007/s10853-013-7380-z	journal	April 2013
Electrochemical impedance of electrolyte/electrode interfaces of lithium-ion rechargeable batteries Itagaki, Masayuki; Yotsuda, Sachiko; Kobari, Nao Electrochimica Acta, Vol. 51, Issue 8-9 https://doi.org/10.1016/j.electacta.2005.02.136	journal	January 2006
The origin of high electrolyte–electrode interfacial resistances in lithium cells containing garnet type solid electrolytes Cheng, Lei; Crumlin, Ethan J.; Chen, Wei Phys. Chem. Chem. Phys., Vol. 16, Issue 34 https://doi.org/10.1039/C4CP02921F	journal	January 2014
Initial stages of oxide formation on the Zr surface at low oxygen pressure: An in situ FIM and XPS study Bespalov, I.; Datler, M.; Buhr, S. Ultramicroscopy, Vol. 159 https://doi.org/10.1016/j.ultramic.2015.02.016	journal	December 2015
Garnet Electrolytes for Solid State Batteries: Visualization of Moisture-Induced Chemical Degradation and Revealing Its Impact on the Li-Ion Dynamics Brugge, Rowena H.; Hekselman, A. K. Ola; Cavallaro, Andrea Chemistry of Materials, Vol. 30, Issue 11 https://doi.org/10.1021/acs.chemmater.8b00486	journal	May 2018
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
A solid future for battery development Janek, Jürgen; Zeier, Wolfgang G. Nature Energy, Vol. 1, Issue 9 https://doi.org/10.1038/nenergy.2016.141	journal	September 2016
The role of the solid electrolyte interphase layer in preventing Li dendrite growth in solid-state batteries Wu, Bingbin; Wang, Shanyu; Lochala, Joshua Energy & Environmental Science, Vol. 11, Issue 7 https://doi.org/10.1039/C8EE00540K	journal	January 2018
Interrelationships among Grain Size, Surface Composition, Air Stability, and Interfacial Resistance of Al-Substituted Li ₇ La ₃ Zr ₂ O ₁₂ Solid Electrolytes Cheng, Lei; Wu, Cheng Hao; Jarry, Angelique ACS Applied Materials & Interfaces, Vol. 7, Issue 32 https://doi.org/10.1021/acsami.5b02528	journal	August 2015
Interfacial Stability of Li Metal–Solid Electrolyte Elucidated via in Situ Electron Microscopy Ma, Cheng; Cheng, Yongqiang; Yin, Kuibo Nano Letters, Vol. 16, Issue 11 https://doi.org/10.1021/acs.nanolett.6b03223	journal	October 2016
Impact of air exposure and surface chemistry on Li–Li ₇ La ₃ Zr ₂ O ₁₂ interfacial resistance Sharafi, Asma; Yu, Seungho; Naguib, Michael Journal of Materials Chemistry A, Vol. 5, Issue 26 https://doi.org/10.1039/C7TA03162A	journal	January 2017
On the determination of atomic charge via ESCA including application to organometallics Sleigh, Christopher; Pijpers, A. P.; Jaspers, Alex Journal of Electron Spectroscopy and Related Phenomena, Vol. 77, Issue 1 https://doi.org/10.1016/0368-2048(95)02392-5	journal	February 1996
Electrochemical Stability of Li6.5La3Zr1.5M0.5O12 (M = Nb or Ta) against Metallic Lithium Kim, Yunsung; Yoo, Aeri; Schmidt, Robert Frontiers in Energy Research, Vol. 4 https://doi.org/10.3389/fenrg.2016.00020	journal	May 2016
Resolving the Grain Boundary and Lattice Impedance of Hot-Pressed Li ₇ La ₃ Zr ₂ O ₁₂ Garnet Electrolytes Tenhaeff, Wyatt E.; Rangasamy, Ezhiyl; Wang, Yangyang ChemElectroChem, Vol. 1, Issue 2 https://doi.org/10.1002/celc.201300022	journal	July 2013
Surface Chemistry Mechanism of Ultra-Low Interfacial Resistance in the Solid-State Electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ Sharafi, Asma; Kazyak, Eric; Davis, Andrew L. Chemistry of Materials, Vol. 29, Issue 18 https://doi.org/10.1021/acs.chemmater.7b03002	journal	September 2017
Electrochemical Window of the Li-Ion Solid Electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ Thompson, Travis; Yu, Seungho; Williams, Logan ACS Energy Letters, Vol. 2, Issue 2 https://doi.org/10.1021/acsenergylett.6b00593	journal	January 2017
Effect of Pore Connectivity on Li Dendrite Propagation within LLZO Electrolytes Observed with Synchrotron X-ray Tomography Shen, Fengyu; Dixit, Marm B.; Xiao, Xianghui ACS Energy Letters, Vol. 3, Issue 4 https://doi.org/10.1021/acsenergylett.8b00249	journal	March 2018
The role of Al and Li concentration on the formation of cubic garnet solid electrolyte of nominal composition Li₇La₃Zr₂O₁₂ Rangasamy, Ezhiyl; Wolfenstine, Jeff; Sakamoto, Jeffrey Solid State Ionics, Vol. 206, p. 28-32 https://doi.org/10.1016/j.ssi.2011.10.022	journal	January 2012
Lithium battery chemistries enabled by solid-state electrolytes Manthiram, Arumugam; Yu, Xingwen; Wang, Shaofei Nature Reviews Materials, Vol. 2, Issue 4 https://doi.org/10.1038/natrevmats.2016.103	journal	February 2017
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets Chen, Ruyi; Cui, Qirui; Liao, Liyang Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23414-3	journal	May 2021
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect Tatemizo, Nobuyuki; Imada, Saki; Okahara, Kizuna Scientific Reports, Vol. 10, Issue 1 https://doi.org/10.1038/s41598-020-58835-5	journal	February 2020

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