Crystal Orientation-Dependent Reactivity of Oxide Surfaces in Contact with Lithium Metal
Abstract
Understanding ionic transport across interfaces between dissimilar materials and the intrinsic chemical stability of such interfaces is a fundamental challenge spanning many disciplines and is of particular importance for designing conductive and stable solid electrolytes for solid-state Li-ion batteries. In this work, we establish a surface science-based approach for assessing the intrinsic stability of oxide materials in contact with Li metal. Through a combination of experimental and computational insights, using Nb-doped SrTiO3 (Nb/STO) single crystals as a model system, we were able to understand the impact of crystallographic orientation and surface morphology on the extent of the chemical reactions that take place between surface Nb, Ti, and Sr upon reaction with Li. By expanding our approach to investigate the intrinsic stability of the technologically relevant, polycrystalline Nb-doped lithium lanthanum zirconium oxide (Li6.5La3Zr1.5Nb0.5O12) system, we found that this material reacts with Li metal through the reduction of Nb, similar to that observed for Nb/STO. These results clearly demonstrate the feasibility of our approach to assess the intrinsic (in)stability of oxide materials for solid-state batteries and point to new strategies for understanding the performance of such systems.
- Authors:
-
[1];
[1];
[2];
[1];
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Univ. of Michigan, Ann Arbor, MI (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); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
- OSTI Identifier:
- 1455046
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Applied Materials and Interfaces
- Additional Journal Information:
- Journal Volume: 10; Journal Issue: 20; Journal ID: ISSN 1944-8244
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; Li metal; buried interface; model system; reactivity; solid electrolytes; solid-state batteries; surface science
Citation Formats
Connell, Justin G., Zhu, Yisi, Zapol, Peter, Tepavcevic, Sanja, Sharafi, Asma, Sakamoto, Jeff, Curtiss, Larry A., Fong, Dillon D., Freeland, John W., and Markovic, Nenad M.. Crystal Orientation-Dependent Reactivity of Oxide Surfaces in Contact with Lithium Metal. United States: N. p., 2018.
Web. doi:10.1021/acsami.8b03078.
Connell, Justin G., Zhu, Yisi, Zapol, Peter, Tepavcevic, Sanja, Sharafi, Asma, Sakamoto, Jeff, Curtiss, Larry A., Fong, Dillon D., Freeland, John W., & Markovic, Nenad M.. Crystal Orientation-Dependent Reactivity of Oxide Surfaces in Contact with Lithium Metal. United States. https://doi.org/10.1021/acsami.8b03078
Connell, Justin G., Zhu, Yisi, Zapol, Peter, Tepavcevic, Sanja, Sharafi, Asma, Sakamoto, Jeff, Curtiss, Larry A., Fong, Dillon D., Freeland, John W., and Markovic, Nenad M.. Mon .
"Crystal Orientation-Dependent Reactivity of Oxide Surfaces in Contact with Lithium Metal". United States. https://doi.org/10.1021/acsami.8b03078. https://www.osti.gov/servlets/purl/1455046.
@article{osti_1455046,
title = {Crystal Orientation-Dependent Reactivity of Oxide Surfaces in Contact with Lithium Metal},
author = {Connell, Justin G. and Zhu, Yisi and Zapol, Peter and Tepavcevic, Sanja and Sharafi, Asma and Sakamoto, Jeff and Curtiss, Larry A. and Fong, Dillon D. and Freeland, John W. and Markovic, Nenad M.},
abstractNote = {Understanding ionic transport across interfaces between dissimilar materials and the intrinsic chemical stability of such interfaces is a fundamental challenge spanning many disciplines and is of particular importance for designing conductive and stable solid electrolytes for solid-state Li-ion batteries. In this work, we establish a surface science-based approach for assessing the intrinsic stability of oxide materials in contact with Li metal. Through a combination of experimental and computational insights, using Nb-doped SrTiO3 (Nb/STO) single crystals as a model system, we were able to understand the impact of crystallographic orientation and surface morphology on the extent of the chemical reactions that take place between surface Nb, Ti, and Sr upon reaction with Li. By expanding our approach to investigate the intrinsic stability of the technologically relevant, polycrystalline Nb-doped lithium lanthanum zirconium oxide (Li6.5La3Zr1.5Nb0.5O12) system, we found that this material reacts with Li metal through the reduction of Nb, similar to that observed for Nb/STO. These results clearly demonstrate the feasibility of our approach to assess the intrinsic (in)stability of oxide materials for solid-state batteries and point to new strategies for understanding the performance of such systems.},
doi = {10.1021/acsami.8b03078},
journal = {ACS Applied Materials and Interfaces},
number = 20,
volume = 10,
place = {United States},
year = {2018},
month = {4}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 7 works
Citation information provided by
Web of Science
Web of Science
Figures / Tables:
Figure 1: (a) LEED and (b) AFM images of an etched and annealed STO(001) surface. (c) AFM image of the same STO(001) surface after Li deposition. Scale bars are 1 μm and height scale units are nm. (d-f) XPS core level spectra before (red) and after (blue) Li deposition showmore »
All figures and tables
(5 total)
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:
The missing memristor found
journal, May 2008
- Strukov, Dmitri B.; Snider, Gregory S.; Stewart, Duncan R.
- Nature, Vol. 453, Issue 7191
Evolution of the electrochemical interface in high-temperature fuel cells and electrolysers
journal, January 2016
- Irvine, John T. S.; Neagu, Dragos; Verbraeken, Maarten C.
- Nature Energy, Vol. 1, Issue 1
Electrolytes and Interphases in Li-Ion Batteries and Beyond
journal, October 2014
- Xu, Kang
- Chemical Reviews, Vol. 114, Issue 23
The energy-storage frontier: Lithium-ion batteries and beyond
journal, November 2015
- Crabtree, George; Kócs, Elizabeth; Trahey, Lynn
- MRS Bulletin, Vol. 40, Issue 12
Issues and challenges facing rechargeable lithium batteries
journal, November 2001
- Tarascon, J.-M.; Armand, M.
- Nature, Vol. 414, Issue 6861, p. 359-367
Lithium-Ion Batteries: Solid Electrolyte: the Key for High-Voltage Lithium Batteries (Adv. Energy Mater. 4/2015)
journal, February 2015
- Li, Juchuan; Ma, Cheng; Chi, Miaofang
- Advanced Energy Materials, Vol. 5, Issue 4
Reviving the lithium metal anode for high-energy batteries
journal, March 2017
- Lin, Dingchang; Liu, Yayuan; Cui, Yi
- Nature Nanotechnology, Vol. 12, Issue 3
All-Solid-State Lithium-Ion Microbatteries: A Review of Various Three-Dimensional Concepts
journal, November 2010
- Oudenhoven, Jos F. M.; Baggetto, Loïc.; Notten, Peter H. L.
- Advanced Energy Materials, Vol. 1, Issue 1
Garnet-type solid-state fast Li ion conductors for Li batteries: critical review
journal, January 2014
- Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana
- Chemical Society Reviews, Vol. 43, Issue 13
A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries
journal, September 2010
- Verma, Pallavi; Maire, Pascal; Novák, Petr
- Electrochimica Acta, Vol. 55, Issue 22, p. 6332-6341
Intergranular Li metal propagation through polycrystalline Li6.25Al0.25La3Zr2O12 ceramic electrolyte
journal, January 2017
- Cheng, Eric Jianfeng; Sharafi, Asma; Sakamoto, Jeff
- Electrochimica Acta, Vol. 223
Mechanism of Lithium Metal Penetration through Inorganic Solid Electrolytes
journal, July 2017
- Porz, Lukas; Swamy, Tushar; Sheldon, Brian W.
- Advanced Energy Materials, Vol. 7, Issue 20
Functional links between stability and reactivity of strontium ruthenate single crystals during oxygen evolution
journal, June 2014
- Chang, Seo Hyoung; Danilovic, Nemanja; Chang, Kee-Chul
- Nature Communications, Vol. 5, Issue 1
Energy and fuels from electrochemical interfaces
journal, December 2016
- Stamenkovic, Vojislav R.; Strmcnik, Dusan; Lopes, Pietro P.
- Nature Materials, Vol. 16, Issue 1
Degradation of NASICON-Type Materials in Contact with Lithium Metal: Formation of Mixed Conducting Interphases (MCI) on Solid Electrolytes
journal, October 2013
- Hartmann, Pascal; Leichtweiss, Thomas; Busche, Martin R.
- The Journal of Physical Chemistry C, Vol. 117, Issue 41
Interphase formation on lithium solid electrolytes—An in situ approach to study interfacial reactions by photoelectron spectroscopy
journal, October 2015
- Wenzel, Sebastian; Leichtweiss, Thomas; Krüger, Dominik
- Solid State Ionics, Vol. 278
Direct Observation of the Interfacial Instability of the Fast Ionic Conductor Li 10 GeP 2 S 12 at the Lithium Metal Anode
journal, March 2016
- Wenzel, Sebastian; Randau, Simon; Leichtweiß, Thomas
- Chemistry of Materials, Vol. 28, Issue 7
Evidence of the chemical stability of the garnet-type solid electrolyte Li5La3Ta2O12 towards lithium by a surface science approach
journal, October 2017
- Fingerle, Mathias; Loho, Christoph; Ferber, Thimo
- Journal of Power Sources, Vol. 366
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
In Situ STEM-EELS Observation of Nanoscale Interfacial Phenomena in All-Solid-State Batteries
journal, May 2016
- Wang, Ziying; Santhanagopalan, Dhamodaran; Zhang, Wei
- Nano Letters, Vol. 16, Issue 6
Universal Ti-rich termination of atomically flat SrTiO3 (001), (110), and (111) surfaces
journal, January 2011
- Biswas, A.; Rossen, P. B.; Yang, C. -H.
- Applied Physics Letters, Vol. 98, Issue 5
Controlling the Relative Areas of Photocathodic and Photoanodic Terraces on the SrTiO 3 (111) Surface
journal, July 2016
- Zhu, Yisi; Salvador, Paul A.; Rohrer, Gregory S.
- Chemistry of Materials, Vol. 28, Issue 14
Controlling the termination and photochemical reactivity of the SrTiO 3 (110) surface
journal, January 2017
- Zhu, Yisi; Salvador, Paul A.; Rohrer, Gregory S.
- Physical Chemistry Chemical Physics, Vol. 19, Issue 11
Atomically flat SrO-terminated SrTiO3(001) substrate
journal, October 2009
- Bachelet, R.; Sánchez, F.; Palomares, F. J.
- Applied Physics Letters, Vol. 95, Issue 14
Lithium Intercalation in Nanoporous Anatase TiO 2 Studied with XPS
journal, April 1997
- Södergren, Sven; Siegbahn, Hans; Rensmo, Håkan
- The Journal of Physical Chemistry B, Vol. 101, Issue 16
Reduction of oxides of iron, cobalt, titanium and niobium by low-energy ion bombardment
journal, August 1989
- Choudhury, T.; Saied, S. O.; Sullivan, J. L.
- Journal of Physics D: Applied Physics, Vol. 22, Issue 8
Engineered Mott ground state in a LaTiO3+δ/LaNiO3 heterostructure
journal, January 2016
- Cao, Yanwei; Liu, Xiaoran; Kareev, M.
- Nature Communications, Vol. 7, Issue 1
Orbital Reconstruction and Covalent Bonding at an Oxide Interface
journal, November 2007
- Chakhalian, J.; Freeland, J. W.; Habermeier, H. -U.
- Science, Vol. 318, Issue 5853
Visualizing short-range charge transfer at the interfaces between ferromagnetic and superconducting oxides
journal, August 2013
- Chien, Te Yu; Kourkoutis, Lena F.; Chakhalian, Jak
- Nature Communications, Vol. 4, Issue 1
A homologous series of structures on the surface of SrTiO3(110)
journal, February 2010
- Enterkin, James A.; Subramanian, Arun K.; Russell, Bruce C.
- Nature Materials, Vol. 9, Issue 3
Lithium Insertion in Nanostructured TiO 2 (B) Architectures
journal, June 2012
- Dylla, Anthony G.; Henkelman, Graeme; Stevenson, Keith J.
- Accounts of Chemical Research, Vol. 46, Issue 5
Lithium adsorption on the SrTiO 3 (100) surface
journal, July 2007
- Mori, E. E.; Kamaratos, M.
- Journal of Physics: Condensed Matter, Vol. 19, Issue 35
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
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
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
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
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
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
Lithium Coordination Sites in Li x TiO 2 (B): A Structural and Computational Study
journal, December 2010
- Armstrong, A. Robert; Arrouvel, Corinne; Gentili, Valentina
- Chemistry of Materials, Vol. 22, Issue 23
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
Surface structure of SrTiO3(100)
journal, September 2003
- Kubo, T.; Nozoye, H.
- Surface Science, Vol. 542, Issue 3
Reconstructions on the polar (110) surface: Analysis using STM, LEED, and AES
journal, June 2008
- Russell, Bruce C.; Castell, Martin R.
- Physical Review B, Vol. 77, Issue 24
Works referencing / citing this record:
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
Figures / Tables found in this record:
Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.