Lithium Expulsion from the Solid-State Electrolyte Li_6.4La₃Zr_1.4Ta_0.6O₁₂ by Controlled Electron Injection in a SEM

The garnet ionic conductor is one of the promising candidate electrolytes for all-solid-state secondary lithium batteries, thanks to its high lithium ion conductivity and good thermal and chemical stability. However, its microstructure is difficult to approach because it is very sensitive to the inquisitive electron beam. In this study based on a scanning electron microscope (SEM), we found that the electron beam expulses the lithium out of Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO), and the expulsed zone expands to where a stationary beam could extend and penetrate. The expulsion of metallic lithium was confirmed by its oxidation reaction after nitrogen inflow into the SEM. This phenomenon may provide us an effective probe to peer into the conductive nature of this electrolyte. A frame-scan scheme is employed to measure the expulsion rate by controllable and more uniform incidence of electrons. Lithium accumulation processes are continuously recorded and classified into four modes by fitting its growth behaviors into a dynamic equation that is mainly related to the initial ion concentration and ion migration rate in the electrolyte. These results open a novel possibility of using the SEM probe to gain dynamic information on ion migration and lithium metal growth in solid materials.