Crystal Orientation-Dependent Reactivity of Oxide Surfaces in Contact with Lithium Metal

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.

doi:10.1021/acsami.8b03078

Title: Crystal Orientation-Dependent Reactivity of Oxide Surfaces in Contact with Lithium Metal

Journal Article · Mon Apr 30 00:00:00 EDT 2018 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.8b03078· OSTI ID:1455046

^[1]; Zhu, Yisi ^[1];

^[1]; Tepavcevic, Sanja ^[1];

^[2]; Sakamoto, Jeff ^[2];

^[1]; Fong, Dillon D. ^[1]; Freeland, John W. ^[1]; Markovic, Nenad M. ^[1]

Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Michigan, Ann Arbor, MI (United States)

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.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1455046

Journal Information:: ACS Applied Materials and Interfaces, Vol. 10, Issue 20; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 7 works

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References (42)

The missing memristor found Strukov, Dmitri B.; Snider, Gregory S.; Stewart, Duncan R. Nature, Vol. 453, Issue 7191 https://doi.org/10.1038/nature06932	journal	May 2008
Evolution of the electrochemical interface in high-temperature fuel cells and electrolysers Irvine, John T. S.; Neagu, Dragos; Verbraeken, Maarten C. Nature Energy, Vol. 1, Issue 1 https://doi.org/10.1038/nenergy.2015.14	journal	January 2016
Electrolytes and Interphases in Li-Ion Batteries and Beyond Xu, Kang Chemical Reviews, Vol. 114, Issue 23 https://doi.org/10.1021/cr500003w	journal	October 2014
The energy-storage frontier: Lithium-ion batteries and beyond Crabtree, George; Kócs, Elizabeth; Trahey, Lynn MRS Bulletin, Vol. 40, Issue 12 https://doi.org/10.1557/mrs.2015.259	journal	November 2015
Issues and challenges facing rechargeable lithium batteries Tarascon, J.-M.; Armand, M. Nature, Vol. 414, Issue 6861, p. 359-367 https://doi.org/10.1038/35104644	journal	November 2001
Lithium-Ion Batteries: Solid Electrolyte: the Key for High-Voltage Lithium Batteries (Adv. Energy Mater. 4/2015) Li, Juchuan; Ma, Cheng; Chi, Miaofang Advanced Energy Materials, Vol. 5, Issue 4 https://doi.org/10.1002/aenm.201570018	journal	February 2015
Reviving the lithium metal anode for high-energy batteries Lin, Dingchang; Liu, Yayuan; Cui, Yi Nature Nanotechnology, Vol. 12, Issue 3 https://doi.org/10.1038/nnano.2017.16	journal	March 2017
All-Solid-State Lithium-Ion Microbatteries: A Review of Various Three-Dimensional Concepts Oudenhoven, Jos F. M.; Baggetto, Loïc.; Notten, Peter H. L. Advanced Energy Materials, Vol. 1, Issue 1 https://doi.org/10.1002/aenm.201000002	journal	November 2010
Garnet-type solid-state fast Li ion conductors for Li batteries: critical review Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana Chemical Society Reviews, Vol. 43, Issue 13 https://doi.org/10.1039/c4cs00020j	journal	January 2014
A review of the features and analyses of the solid electrolyte interphase in Li-ion batteries Verma, Pallavi; Maire, Pascal; Novák, Petr Electrochimica Acta, Vol. 55, Issue 22, p. 6332-6341 https://doi.org/10.1016/j.electacta.2010.05.072	journal	September 2010
Intergranular Li metal propagation through polycrystalline Li6.25Al0.25La3Zr2O12 ceramic electrolyte Cheng, Eric Jianfeng; Sharafi, Asma; Sakamoto, Jeff Electrochimica Acta, Vol. 223 https://doi.org/10.1016/j.electacta.2016.12.018	journal	January 2017
Mechanism of Lithium Metal Penetration through Inorganic Solid Electrolytes Porz, Lukas; Swamy, Tushar; Sheldon, Brian W. Advanced Energy Materials, Vol. 7, Issue 20 https://doi.org/10.1002/aenm.201701003	journal	July 2017
Functional links between stability and reactivity of strontium ruthenate single crystals during oxygen evolution Chang, Seo Hyoung; Danilovic, Nemanja; Chang, Kee-Chul Nature Communications, Vol. 5, Issue 1 https://doi.org/10.1038/ncomms5191	journal	June 2014
Energy and fuels from electrochemical interfaces Stamenkovic, Vojislav R.; Strmcnik, Dusan; Lopes, Pietro P. Nature Materials, Vol. 16, Issue 1 https://doi.org/10.1038/nmat4738	journal	December 2016
Degradation of NASICON-Type Materials in Contact with Lithium Metal: Formation of Mixed Conducting Interphases (MCI) on Solid Electrolytes Hartmann, Pascal; Leichtweiss, Thomas; Busche, Martin R. The Journal of Physical Chemistry C, Vol. 117, Issue 41 https://doi.org/10.1021/jp4051275	journal	October 2013
Interphase formation on lithium solid electrolytes—An in situ approach to study interfacial reactions by photoelectron spectroscopy Wenzel, Sebastian; Leichtweiss, Thomas; Krüger, Dominik Solid State Ionics, Vol. 278 https://doi.org/10.1016/j.ssi.2015.06.001	journal	October 2015
Direct Observation of the Interfacial Instability of the Fast Ionic Conductor Li ₁₀ GeP ₂ S ₁₂ at the Lithium Metal Anode Wenzel, Sebastian; Randau, Simon; Leichtweiß, Thomas Chemistry of Materials, Vol. 28, Issue 7 https://doi.org/10.1021/acs.chemmater.6b00610	journal	March 2016
Evidence of the chemical stability of the garnet-type solid electrolyte Li5La3Ta2O12 towards lithium by a surface science approach Fingerle, Mathias; Loho, Christoph; Ferber, Thimo Journal of Power Sources, Vol. 366 https://doi.org/10.1016/j.jpowsour.2017.08.109	journal	October 2017
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
In Situ STEM-EELS Observation of Nanoscale Interfacial Phenomena in All-Solid-State Batteries Wang, Ziying; Santhanagopalan, Dhamodaran; Zhang, Wei Nano Letters, Vol. 16, Issue 6 https://doi.org/10.1021/acs.nanolett.6b01119	journal	May 2016
Universal Ti-rich termination of atomically flat SrTiO3 (001), (110), and (111) surfaces Biswas, A.; Rossen, P. B.; Yang, C. -H. Applied Physics Letters, Vol. 98, Issue 5 https://doi.org/10.1063/1.3549860	journal	January 2011
Controlling the Relative Areas of Photocathodic and Photoanodic Terraces on the SrTiO ₃ (111) Surface Zhu, Yisi; Salvador, Paul A.; Rohrer, Gregory S. Chemistry of Materials, Vol. 28, Issue 14 https://doi.org/10.1021/acs.chemmater.6b02205	journal	July 2016
Controlling the termination and photochemical reactivity of the SrTiO ₃ (110) surface Zhu, Yisi; Salvador, Paul A.; Rohrer, Gregory S. Physical Chemistry Chemical Physics, Vol. 19, Issue 11 https://doi.org/10.1039/C6CP08608J	journal	January 2017
Atomically flat SrO-terminated SrTiO3(001) substrate Bachelet, R.; Sánchez, F.; Palomares, F. J. Applied Physics Letters, Vol. 95, Issue 14 https://doi.org/10.1063/1.3240869	journal	October 2009
Lithium Intercalation in Nanoporous Anatase TiO ₂ Studied with XPS Södergren, Sven; Siegbahn, Hans; Rensmo, Håkan The Journal of Physical Chemistry B, Vol. 101, Issue 16 https://doi.org/10.1021/jp9639399	journal	April 1997
Reduction of oxides of iron, cobalt, titanium and niobium by low-energy ion bombardment Choudhury, T.; Saied, S. O.; Sullivan, J. L. Journal of Physics D: Applied Physics, Vol. 22, Issue 8 https://doi.org/10.1088/0022-3727/22/8/026	journal	August 1989
Engineered Mott ground state in a LaTiO3+δ/LaNiO3 heterostructure Cao, Yanwei; Liu, Xiaoran; Kareev, M. Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms10418	journal	January 2016
Orbital Reconstruction and Covalent Bonding at an Oxide Interface Chakhalian, J.; Freeland, J. W.; Habermeier, H. -U. Science, Vol. 318, Issue 5853 https://doi.org/10.1126/science.1149338	journal	November 2007
Visualizing short-range charge transfer at the interfaces between ferromagnetic and superconducting oxides Chien, Te Yu; Kourkoutis, Lena F.; Chakhalian, Jak Nature Communications, Vol. 4, Issue 1 https://doi.org/10.1038/ncomms3336	journal	August 2013
A homologous series of structures on the surface of SrTiO3(110) Enterkin, James A.; Subramanian, Arun K.; Russell, Bruce C. Nature Materials, Vol. 9, Issue 3 https://doi.org/10.1038/nmat2636	journal	February 2010
Lithium Insertion in Nanostructured TiO ₂ (B) Architectures Dylla, Anthony G.; Henkelman, Graeme; Stevenson, Keith J. Accounts of Chemical Research, Vol. 46, Issue 5 https://doi.org/10.1021/ar300176y	journal	June 2012
Lithium adsorption on the SrTiO ₃ (100) surface Mori, E. E.; Kamaratos, M. Journal of Physics: Condensed Matter, Vol. 19, Issue 35 https://doi.org/10.1088/0953-8984/19/35/356001	journal	July 2007
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
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
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
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
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
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
Lithium Coordination Sites in Li _x TiO ₂ (B): A Structural and Computational Study Armstrong, A. Robert; Arrouvel, Corinne; Gentili, Valentina Chemistry of Materials, Vol. 22, Issue 23 https://doi.org/10.1021/cm102589x	journal	December 2010
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
Surface structure of SrTiO3(100) Kubo, T.; Nozoye, H. Surface Science, Vol. 542, Issue 3 https://doi.org/10.1016/S0039-6028(03)00998-1	journal	September 2003
Reconstructions on the polar $Sr Ti O_{3}$ (110) surface: Analysis using STM, LEED, and AES Russell, Bruce C.; Castell, Martin R. Physical Review B, Vol. 77, Issue 24 https://doi.org/10.1103/PhysRevB.77.245414	journal	June 2008

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