Degradation of a lithium cobalt oxide cathode under high voltage operation at an interface with an oxide solid electrolyte

Ito, Kotaro*; Tamura, Kazuhisa   ; Shimizu, Keisuke*; Yamada, Norifumi*; Watanabe, Kenta*; Suzuki, Kota*; Kanno, Ryoji*; Hirayama, Masaaki*

LiCoO is widely used as a cathode material in lithium-ion batteries. However, the reversible capacity of LiCoO at high voltage is not well known because of the oxidative degradation of the electrolyte. In this study, a thin-film all-solid-state battery was fabricated with epitaxially grown LiCoO cathode and LiPO solid electrolyte as a model battery that operates stably at high voltages, ranging up to 4.6 V, without drastic degradation. However, the charge-discharge capacities of the battery decreased with cycling at 4.7 V. synchrotron X-ray diffraction studies revealed that LiCoO was deactivated via a change in its crystal structure to O1 type, with narrow interlayer distances, at 4.7 V. The reduced distance between the interlayers in the O1 structure possibly prevents the re-intercalation of Li ions, leading to irreversibility.