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 et al. · Nano Lett · 2024

basic_science · Level V

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Abstract

Lithium-metal (Li<sup>0</sup>) 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 <i>operando</i> 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, Li<sup>0</sup>, and graphite-intercalation compounds. During charging, Li<sup>+</sup> preferentially deposited at the Li-graphite|SE interface. Upon further plating, Li<sup>0</sup>-dendrites formed, inducing short circuits and the reverse migration of Li<sup>0</sup>. 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<sup>+</sup> and Li<sup>0</sup> in the interlayer is governed by multiple competing factors.