Mechanism of the Loss of Capacity of LiNiO₂ Electrodes for Use in Aqueous Li-Ion Batteries: Unveiling a Fundamental Cause of Deterioration in an Aqueous Electrolyte through In Situ Raman Observation

This study investigated the fundamental mechanisms of the loss of capacity of LiNiO2 (LNO) electrodes for Li+ insertion/deinsertion with a special focus on the origin of this deterioration in an aqueous system. In situ Raman spectra revealed that the intercalation of H+ ions formed a NiOOHx film at the surface of LNO during the initial electrochemical cycles; this NiOOHx film was also confirmed by X-ray photoelectron spectroscopy and transmission electron microscopy analysis. The formation of an electrochemically inactive spinel-like phase (Ni3O4) at the subsurface was triggered by the absence of Li in the NiOOHx film at the surface. These structural changes of LNO, accelerated by the intercalation of H+ ions, were considered to be the fundamental cause of the greater loss of capacity in the aqueous system.