Li Dynamics in Mixed Ionic-Electronic Conducting Interlayer of All-Solid-State Li-metal Batteries

Cao, Daxian; Zhang, Yuxuan; Ji, Tongtai; Zhao, Xianhui; Cakmak, Ercan; Ozcan, Soydan; Geiwitz, Michael; Bilheux, Jean-Christophe; Xu, Kang; Wang, Ying; Burch, Kenneth Stephen; Tu, Qingsong Howard; Zhu, Hongli

doi:10.1021/acs.nanolett.3c04072

Li Dynamics in Mixed Ionic-Electronic Conducting Interlayer of All-Solid-State Li-metal Batteries

Journal Article · Thu Jan 25 00:00:00 EST 2024 · Nano Letters

DOI:https://doi.org/10.1021/acs.nanolett.3c04072· OSTI ID:2282796

Cao, Daxian ^[1]; ^[2]; Ji, Tongtai ^[1]; ^[2]; ^[2]; Ozcan, Soydan ^[2]; Geiwitz, Michael ^[3]; ^[2]; Xu, Kang ^[4]; ^[1]; ^[3]; Tu, Qingsong Howard ^[5]; ^[1]

Northeastern Univ., Boston, MA (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Boston College, Chestnut Hill, MA (United States)
Army Research Lab., Adelphi, MD (United States)
Rochester Inst. of Technology, Rochester, NY (United States)

Lithium–metal (Li⁰) anodes potentially enable all-solid-state batteries with high energy density. However, it shows incompatibility with sulfide solid-state electrolytes (SEs). One strategy is introducing an interlayer, generally made of a mixed ionic-electronic conductor (MIEC). Yet, how Li behaves within MIEC remains unknown. Herein, we investigated the Li dynamics in a graphite interlayer, a typical MIEC, by using operando neutron imaging and Raman spectroscopy. This study revealed that intercalation-extrusion-dominated mechanochemical reactions during cell assembly transform the graphite into a Li-graphite interlayer consisting of SE, Li⁰, and graphite-intercalation compounds. During charging, Li⁺ preferentially deposited at the Li-graphite|SE interface. Upon further plating, Li⁰-dendrites formed, inducing short circuits and the reverse migration of Li⁰. Modeling indicates the interface has the lowest nucleation barrier, governing lithium transport paths. Our study elucidates intricate mechano-chemo-electrochemical processes in mixed conducting interlayers. The behavior of Li⁺ and Li⁰ in the interlayer is governed by multiple competing factors.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). High Flux Isotope Reactor (HFIR); Northeastern Univ., Boston, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC05-00OR22725; SC0024528; SC0018675; DMR-2003343

OSTI ID:: 2282796

Alternate ID(s):: OSTI ID: 2283884; OSTI ID: 2293547

Journal Information:: Nano Letters, Vol. 24, Issue 5; ISSN 1530-6984

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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