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

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

Journal Article · Sun Feb 10 00:00:00 EST 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.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE; 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

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1508374

Alternate ID(s):: OSTI ID: 1494204

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

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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