Using Real-Time Electron Microscopy To Explore the Effects of Transition-Metal Composition on the Local Thermal Stability in Charged LixNiyMnzCo1–y–zO2 Cathode Materials

Abstract

In this work, we use in situ transmission electron microscopy (TEM) to investigate the thermal decomposition that occurs at the surface of charged LixNiyMnzCo1–y–zO2 (NMC) cathode materials of different composition (with y, z = 0.8, 0.1, and 0.6, 0.2, and 0.4,and 0.3), after they have been charged to their practical upper limit voltage (4.3 V). By heating these materials inside the TEM, we are able to directly characterize near surface changes in both their electronic structure (using electron energy loss spectroscopy) and crystal structure and morphology (using electron diffraction and bright-field imaging). The most Ni-rich material (y, z = 0.8, 0.1) is found to be thermally unstable at significantly lower temperatures than the other compositions—this is manifested by changes in both the electronic structure and the onset of phase transitions at temperatures as low as 100 °C. Electron energy loss spectroscopy indicates that (i) the thermally induced reduction of Ni ions drives these changes, and (ii) th...