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Title: 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:
ORCiD logo [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [2];  [2]; ORCiD logo [1];  [1];  [1];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. 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) (SC-22); 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. 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., and Markovic, Nenad M. Mon . "Crystal Orientation-Dependent Reactivity of Oxide Surfaces in Contact with Lithium Metal". United States. doi: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}
}

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Figures / Tables:

Figure 1 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 » (d) the clear presence of both Li metal and Li-O species, (e) the reduction of Ti4+ to Ti3+ and Ti2+ and (f) the reduction of Nb5+ to Nb4+ after Li deposition. Increased noise in the Ti 2p and Nb 3d core level spectra after Li deposition is due to signal attenuation by the Li overlayer.« less

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