Doping‐Induced Surface and Grain Boundary Effects in Ni‐Rich Layered Cathode Materials

In this work, the effects of dopant size and oxidation state on the structure and electrochemical performance of LiNi0.8Co0.1Mn0.1O2 (NCM811) are investigated. It is shown that doping with boron (B) which has a small ionic radius and an oxidation state of 3+, leads to the formation of a boron oxide‐containing surface coating (probably Li3BO3), mainly on the outer surface of the secondary particles. Due to this effect, boron only slightly affects the size of the primary particle and the initial capacity, but significantly improves the capacity retention. On the other hand, the dopant ruthenium (Ru) with a larger ionic radius and a higher oxidation state of 5+ can be stabilized within the secondary particles and does not experience a segregation to the outer agglomerate surface. However, the Ru dopant preferentially occupies incoherent grain boundary sites, resulting in smaller primary particle size and initial capacity than for the B‐doped and pristine NCM811. This work demonstrates that a small percentage of dopant (2 mol%) cannot significantly affect bulk properties, but it can strongly influence the surface and/or grain boundary properties of microstructure and thus the overall performance of cathode materials. A small amount of dopant can considerably change the performance of layered oxide Ni‐rich LiNixCoyMn1x−yO2 (NCM) cathode materials for Li‐ion batteries. Depending on its size and oxidation state, a dopant can modify the atomistic structure of agglomerate surface and/or grain boundaries, and thereby, influence the capacity and cyclability of NCM cathodes.