Enhanced electrochemical lithium storage activity of LiCrO2 by size effect

Cr8O21 was chemically lithiated using a lithium-biphenyl-dimethoxyethane solution. Lithiated Cr8O21 shows a structure in which as-formed LiCrO2 units are sandwiched between Cr2O3 superlattice layers. Chemically lithiated Cr8O21 shows a delithiation capacity of 200 mAh g(-1). It means that LiCrO2 units in lithiated Cr8O21 are electrochemically active. This finding is opposite to previous reports that LiCrO2 materials have very poor Li-storage capacities. Our new result implies that LiCrO2 with extremely small domain size could show enhanced reactivity. This proposal is proved unambiguously by the fact that LiCrO2 powder materials with smaller grain size (<20 nm) show much higher capacities than LiCrO2 materials with larger grain size (>50 nm). In addition, it is found that the cation mixing is more significantly in LiCrO2 materials with smaller grain size, which seems a key factor for the storage and transport of lithium in layered Cr-based materials. The cation mixing may also explain the result that the lattice parameters of LiCrO2 do not change significantly upon lithium extraction and insertion, investigated by in situ and ex situ XRD techniques.