Probing the Ni(OH)2 Precursor for LiNiO2 at the Atomic Scale: Insights into the Origin of Structural Defect in a Layered Cathode Active Material

Abstract In lithium ion batteries (LIBs), the layered cathode materials of composition LiNi1−x−yCoxMnyO2 are critical for achieving high energy densities. A high nickel content (>80%) provides an attractive balance between high energy density, long lifetime, and low cost. Consequently, Ni‐rich layered oxides cathode active materials (CAMs) are in high demand, and the importance of LiNiO2 (LNO) as limiting case, is hence paramount. However, achieving perfect stoichiometry is a challenge resulting in various structural issues, which successively impact physicochemical properties and result in the capacity fade of LIBs. To better understand defect formation in LNO, the role of the Ni(OH)2 precursor morphology in the synthesis of LNO requires in‐depth investigation. By employing aberration‐corrected scanning transmission electron microscopy, electron energy loss spectroscopy, and precession electron diffraction, a direct observation of defects in the Ni(OH)2 precursor preparedis reported and the ex situ structural evolution from the precursor to the end product is monitored. During synthesis, the layered Ni(OH)2 structure transforms to partially lithiated (non‐layered) NiO and finally to layered LNO. The results suggest that the defects observed in commercially relevant CAMs originate to a large extent from the precursors, hence care must be taken in tuning the co‐precipitation parameters to synthesize defect‐free Ni‐rich layered oxides CAMs.