High Capacity Li-Rich Positive Electrode Materials with Reduced First-Cycle Irreversible Capacity Loss

The first charge–discharge cycling behaviors of two sets of Li–Ni–Mn–Co type positive electrode materials were compared. The samples in each set have similar Ni–Mn–Co ratios but different Li-to-total metal ratio (Li/M). The samples that were Li-rich with a Li­[Li x M(1–x)]­O2 structure showed a typical 4.5 V “oxygen loss” plateau and a typical irreversible capacity loss near 25%. Surprisingly, other samples with lower Li/M ratios that still exhibited a 4.5 V “oxygen loss” plateau exhibited an irreversible capacity loss as low as 4.0% of their first charge capacity. XRD analysis revealed that all samples were single-phase layered oxides. A separate and a detailed XRD analysis combined with dQ/dV analysis showed that the reduced irreversible capacity loss was not caused by the admixture of a spinel phase. ICP-OES results and the oxidation state versus atomic occupancy rules suggested the presence of metal site vacancies in the pristine materials with low IRC, which were confirmed by densities measured with a helium pycnometer. The results presented here show that the small irreversible capacity is a consequence of (a) metal site vacancies, leading to Li­[□ q M(1–q)]­O2 structures, where □ is a metal site vacancy, which leads to (b) no Li atoms in the transition metal layer. These materials still have Li/M > 1, so they are “Li-rich”, but they are “traditional layered materials” with no Li in the transition metal layer. This study identifies a new route for fabricating high capacity Li-rich positive electrode materials with small irreversible capacity loss.