Kinetic versus Thermodynamic Stability of LLZO in Contact with Lithium Metal

Connell, Justin G.; Fuchs, Till; Hartmann, Hannah; Krauskopf, Thorben; Zhu, Yisi; Sann, Joachim; Garcia-Mendez, Regina; Sakamoto, Jeff; Tepavcevic, Sanja; Janek, Jürgen

doi:10.1021/acs.chemmater.0c03869

Title: Kinetic versus Thermodynamic Stability of LLZO in Contact with Lithium Metal

Journal Article · Mon Nov 30 00:00:00 EST 2020 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.0c03869· OSTI ID:1764985

^[1]; Fuchs, Till ^[2]; Hartmann, Hannah ^[2]; Krauskopf, Thorben ^[2]; Zhu, Yisi ^[1]; Sann, Joachim ^[2]; Garcia-Mendez, Regina ^[3]; Sakamoto, Jeff ^[3]; Tepavcevic, Sanja ^[1];

^[2]

Argonne National Lab. (ANL), Lemont, IL (United States)
Justus-Liebig-University Giessen, Giessen (Germany)
Univ. of Michigan, Ann Arbor, MI (United States)

Li₇La₃Zr₂O₁₂ (LLZO) garnet-based oxides are a promising class of solid electrolytes used as the separator in all-solid-state batteries (ASSBs). While LLZO is considered to have a wide electrochemical stability window, its intrinsic stability in contact with lithium metal is not sufficiently well understood, and there is still a debate on the key question of whether LLZO does or does not form passivation layers before and during cycling. Utilizing both in situ and operando X-ray photoelectron spectroscopy techniques, in this work we reveal the presence of a kinetic barrier to the reduction of LLZO by Li metal, with the extent of oxygen-deficient interphase (ODI) formation depending sensitively on the energetics of Li metal arriving at the Li vertical bar LLZO interface. Despite the clear presence of a kinetic barrier to reduction, the electrochemical response of the Li vertical bar LLZO interface is unchanged by the presence of the ODI, indicating that ODI formation during electrochemical cycling does not hinder charge transfer across the Li vertical bar LLZO interface. Overall, these results reveal that the reactivity of LLZO with Li metal depends not only on the material properties of the adjoining phases (i.e., surface purity and active contact) and their resulting thermodynamic stability but also on the energy input at the interface and the resulting reaction kinetics. Furthermore, the presence of a kinetic barrier to reduction highlights the additional complexities governing the reactivity of solid-state interfaces in ASSBs and underscores the importance of operando characterization of interfacial stability to design more robust, high-performance protection strategies for solid electrolytes in contact with reactive electrodes.

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

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office; German Federal Ministry of Education and Research (BMBF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; Funds of the Chemical Industry (FCI)

Grant/Contract Number:: AC02-06CH11357; 03XP0224E

OSTI ID:: 1764985

Journal Information:: Chemistry of Materials, Vol. 32, Issue 23; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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