In Situ Observation of the Effect of Accelerating Voltage on Electron Beam Damage of Layered Cathode Materials for Lithium-Ion Batteries.

Abstract

Electron beam damage from transmission electron microscopy of layered lithium transition-metal oxides is a threshold phenomenon that depends on the electron beam energy, which we demonstrate in this study by varying the accelerating voltage of a scanning transmission electron microscope. The electron beam irradiation experiment shows that Ni in LiNiO2 has much lower threshold energy for displacement than Co in LiCoO2, which is supported by DFT calculations predicting that Ni has lower migration energy. The transition-metal ions are reduced from the oxidation state of +3 to +2 during migration from their original positions to the lithium sites, and Ni is more easily reduced than Co because of its electronic configuration. In addition, the high-energy electron beam induces oxygen release, which is another symptom of degradation of materials that occurs more strongly in Ni-containing materials with ion displacement.