Tuning Li-enrichment in high-Ni layered oxide cathodes to optimize electrochemical performance for Li-ion battery

To understand what and how structural properties affect battery performance, and to optimize the structural properties accordingly are of crucial importance to improve the performance of cathode materials for advanced Li-ion batteries. Herein, we investigated the influence of Li-enrichment in Li1+x(Ni0.8Co0.2)(1-x)O-2 transition metal (TM) oxide cathodes, obtained by sintering Ni0.8Co0.2(OH)(2) precursor with different amount of Li sources. Compared with stoichiometric Li1+x(Ni0.8Co0.2)(1-x)O-2 (i.e. x = 0, Li:TM = 1:1), the improvements of cycling stability and rate performance were observed in material with moderate degree of Li-enrichment with respect to TMs (i.e. x = 0.019, Li:TM = 1.04:1). Further increase in Li:TM ratio up to 1.07 diminishes the electrochemical performance. Multi-scale structural characterizations including neutron diffraction and aberration-corrected transmission electron microscopy measurements show that the Li-enrichment leads to a monotonical increase in both Li/Ni exchange ratio and Li slab space. Based on the results, we argue that, in material with moderate Li-enrichment, larger Li slab space can facilitate the diffusion of Li ions and a certain amount of Li/Ni disordering can also mitigate the contraction of layered structure, therefore resulting in an optimized electrochemical performance; while in material with excessive Li:TM ratio, the diffusion path can be partially blocked due to the presence of redundant Ni ions in Li layers.