A mechanistic investigation of the Li<sub>10</sub>GeP<sub>2</sub>S<sub>12</sub>|LiNi<sub>1-x-y</sub>Co<sub>x</sub>Mn<sub>y</sub>O<sub>2</sub> interface stability in all-solid-state lithium batteries.

Zuo, Tong-Tong; Rueß, Raffael; Pan, Ruijun; Walther, Felix; Rohnke, Marcus; Hori, Satoshi; Kanno, Ryoji; Schröder, Daniel et al. · Nat Commun · 2021

basic_science · Level V

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Abstract

All-solid-state batteries are intensively investigated, although their performance is not yet satisfactory for large-scale applications. In this context, the combination of Li<sub>10</sub>GeP<sub>2</sub>S<sub>12</sub> solid electrolyte and LiNi<sub>1-x-y</sub>Co<sub>x</sub>Mn<sub>y</sub>O<sub>2</sub> positive electrode active materials is considered promising despite the yet unsatisfactory battery performance induced by the thermodynamically unstable electrode|electrolyte interface. Here, we report electrochemical and spectrometric studies to monitor the interface evolution during cycling and understand the reactivity and degradation kinetics. We found that the Wagner-type model for diffusion-controlled reactions describes the degradation kinetics very well, suggesting that electronic transport limits the growth of the degradation layer formed at the electrode|electrolyte interface. Furthermore, we demonstrate that the rate of interfacial degradation increases with the state of charge and the presence of two oxidation mechanisms at medium (3.7 V vs. Li<sup>+</sup>/Li < E < 4.2 V vs. Li<sup>+</sup>/Li) and high (E ≥ 4.2 V vs. Li<sup>+</sup>/Li) potentials. A high state of charge (>80%) triggers the structural instability and oxygen release at the positive electrode and leads to more severe degradation.