In Situ Liquid Electrochemical TEM Investigation of LiMn1.5Ni0.5O4 Thin Film Cathode for Micro‐Battery Applications

Abstract Micro‐batteries are attractive miniaturized energy devices for new Internet of Things applications, but the lack of understanding of their degradation process during cycling hinders improving their performance. Here focused ion beam (FIB)‐lamella from LiMn 1.5 Ni 0.5 O 4 (LMNO) thin‐film cathode is in situ cycled in a liquid electrolyte inside an electrochemical transmission electron microscope (TEM) holder to analyze structural and morphology changes upon (de)lithiation processes. A high‐quality electrical connection between the platinum (Pt) current collector of FIB‐lamella and the microchip's Pt working electrode is established, as confirmed by local two‐probe conductivity measurements. In situ cyclic voltammetry (CV) experiments show two redox activities at 4.41 and 4.58/4.54 V corresponding to the Ni 2+/3+ and Ni 3+/4+ couples, respectively. (S)TEM investigations of the cycled thin‐film reveal formation of voids and cracks, loss of contact with current collector, and presence of organic decomposition products. The 4D STEM ASTAR technique highlights the emergence of an amorphization process and a decrease in average grain size from 20 to 10 nm in the in situ cycled electrode. The present findings, obtained for the first time through the liquid electrochemical TEM study, provide several insights explaining the capacity fade of the LMNO thin‐film cathode typically observed upon cycling in a conventional liquid electrolyte.