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

Abstract

Li 7La 3Zr 2O 12 (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 stabilitymore » of the LLZO-Li interface.« less

Authors:
 [1]; ORCiD logo [1];  [1];  [1];  [2];  [2];  [2];  [3];  [1];  [1];  [3];  [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States)
  2. Univ. of Michigan, Ann Arbor, MI (United States)
  3. Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (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:
Journal Article: 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. 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., and Markovic, Nenad M. Sun . "Dopant-Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal". United States. doi:10.1002/aenm.201803440.
@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},
issn = {1614-6832},
number = 12,
volume = 9,
place = {United States},
year = {2019},
month = {2}
}

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