Colloidal synthesis of cuprite (Cu₂O) octahedral nanocrystals and their electrochemical lithiation

We report a facile colloidal route to prepare octahedral-shaped cuprite (Cu₂O) nanocrystals (NCs) of ∼40 nm in size that exploits a new reduction pathway, i.e., the controlled reduction of a cupric ion by acetylacetonate directly to cuprite. Detailed structural, morphological, and chemical analyses were carried on the cuprite NCs. We also tested their electrochemical lithiation, using a combination of techniques (cyclic voltammetry, galvanostatic, and impedance spectroscopy), in view of their potential application as anodes for Li ion batteries. Along with these characterizations, the morphological, structural, and chemical analyses (via high-resolution electron microscopy, electron energy loss spectroscopy, and X-ray photoelectron spectroscopy) of the cycled Cu₂O NCs (in the lithiated stage, after ∼50 cycles) demonstrate their partial conversion upon cycling. At this stage, most of the NCs had lost their octahedral shape and had evolved into multidomain particles and were eventually fragmented. Overall, the shape changes (upon cycling) did not appear to be concerted for all the NCs in the sample, suggesting that different subsets of NCs were characterized by different lithiation kinetics. We emphasize that a profound understanding of the lithiation reaction with NCs defined by a specific crystal habit is still essential to optimize nanoscale conversion reactions.