Rechargeable, Ambient-Stable Li-Ion Probe toward In Situ TEM for Electrochemical Dynamics.

Lithium-ion batteries, particularly those employing lithium metal-based anodes, have garnered significant attention as energy storage systems due to their high energy density during charge-discharge cycles. However, the fundamental mechanisms underlying the microstructural evolution during cycling remain insufficiently understood. Here, we introduce a rechargeable Li-ion probe specifically designed for real-time transmission electron microscopy (TEM) analysis of electrode materials. The probe withstands electron beam irradiation and preserves its functionality under ambient conditions, enabling repeated in situ TEM measurements. By applying galvanostatic conditions, we employed this Li-ion probe to visualize (de)lithiation processes in both a lithiophilic LiAu₃ electrode and a lithiophobic Ni electrode. Furthermore, this probe is not limited to specific electrode materials but can be adapted for a wide range of battery components, including cathodes, anodes, and current collectors, making it a versatile tool for advanced energy storage research. Our findings demonstrate that the Li-ion probe facilitates critical insights into the interplay between the electrode microstructure and electrochemical behavior, thereby paving the way for advanced battery characterization techniques. This innovation establishes a foundation for future research aimed at unraveling the dynamic behavior of lithium-based electrodes during prolonged cycling.