Intrinsic Li Distribution in Layered Transition-Metal Oxides Using Low-Dose Scanning Transmission Electron Microscopy and Spectroscopy

Understanding Li distribution in layered lithium transition-metal oxide (LiTMO) cathodes in Li-ion batteries has been a major challenge at the atomic scale and nanoscale. Li is extremely difficult to study by transmission electron microscopy (TEM) because the high-energy electrons impart significant energy and cause massive migration. Here, we directly map the intrinsic spatial distribution and bonding of Li in LiNiO2-layered cathode materials using low-dose and low-loss electron energy loss spectroscopy (EELS). EELS spectra of the Li–K edge are measured simultaneously with O–K and Ni–L, M3,2 edges from layered, cation-mixed, and rock-salt phases and directly matched with atomic-resolution scanning TEM images to correlate the changes in peak intensities and positions to the stoichiometry changes with continual loss of Li and O. Changes in the Li content in the LiNiO2 particles as a function of electron beam dose are studied by sequential Li spectroscopic mapping. We show that the “intrinsic” Li distribution can be observed using a total dose of less than ∼1.5 × 108 e– nm–2 at an accelerating voltage of 80 kV. The method of nanoscale mapping of Li distribution introduced in this study is applicable to high-Ni LiTMO cathode materials (>89% of Ni) as well as LiNiO2. Further study on the extra peaks of the Li–K edge reveals that the peak at ∼59 eV is from the Li ions intercalated in between NiO2 layers barely interacting with each other with less Li K shell electrons pulled to the L shell electrons in NiO2. The results shown here provide improved low-loss TEM characterization approaches that can be used to understand the intrinsic fundamental behaviors in Li-ion batteries.