Rechargeable, Ambient-Stable Li-Ion Probe toward <i>In Situ</i> 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 <i>in situ</i> 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.