All-solid-state lithium metal batteries, poised to deliver one of the highest specific energy among rechargeable batteries, establish themselves as a front-runner for next-generation electric vehicle batteries; nevertheless, realizing high-performance solid-state Li batteries remains challenging due to the high impedance and (for the anode side) uncontrolled Li deposition at the interfaces between active electrode materials and solid electrolytes. The lack of direct and quantitative characterization tools for the active material−electrolyte interfaces has been a major hurdle towards high-performance solid-state batteries. Most studies had to rely on indirect characterization methods to approximate the identity, distribution, and evolution of species and structures at the interfaces. This work demonstrates a combined diagnostics of the interfaces and their evolutions during cell operation using in situ multi-site plasma focused-ion-beam (pFIB) tomography.Utilizing the advanced capabilities of pFIB technology, which offers significantly higher material removal rates compared to gallium-based systems, we significantly reduce the duration of tomography sessions. This efficiency enhancement not only accelerates the morphological data acquisition but also supports the continuous and multi-site application of pFIB tomography on a single specimen through its electrochemical reaction cycle. In this experiment, the Li-electrolyte interface within a trilayer battery structure (Li/electrolyte/NMC-electrolyte composite) was characterized in situ at multiple sites using FIB. The tests were performed in a custom-built transfer vessel equipped with an in situ testing platform, enabling air-free specimen transfer from an argon-filled glovebox to the pFIB-SEM setup. This system also facilitates in situ charge/discharge cycling under simulated real-world conditions, including environmental stimuli like heating and pressing. The open-cell design of the battery specimen on this platform, with exposed and polished interfaces, provides direct visibility into the interface dynamics that is comparable to traditional Swagelok-cell setups but with enhanced observational capabilities.The resultant tomography models from the Li-electrolyte interface during charging and discharging cycles elucidate the structural evolution of the components under different operational statuses. Key observations include the initiation, growth, and interaction of Li dendrites within the electrolyte layer, and the development of voids at the Li-electrolyte interface, particularly their dynamics during battery operation. While these phenomena have been extensively studied using other diagnostic techniques, the application of in situ multi-site pFIB offers unprecedented insights into the morphological changes induced by battery cycling, thereby contributing to a comprehensive understanding of the failure mechanisms in solid-state batteries.
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