Colloidal Cu_(2-x)(S_ySe_(1-y)) alloy nanocrystals with controllable crystal phase: synthesis, plasmonic properties, cation exchange and electrochemical lithiationt

摘要

We report synthetic routes to both cubic and hexagonal phase Cu_(2-x)(S_ySe_(1-y)) alloy nanocrystals exhibiting a well-defined near-infrared valence band plasmon resonance, the spectral position of which is dependent mainly on x, i.e. on Cu stoichiometry, and to a lesser extent on the crystal phase of the NCs. For cubic Cu_(2-x)(S_ySe_(1-y)) nanocrystals y could be varied in the 0.4-0.6 range, while for hexagonal nanocrystals y could be varied in the 0.3-0.7 range. Furthermore, the Cu_(2-x)(S_ySe_(1-y)) nanocrystals could be transformed into the corresponding Cd-based alloy nanocrystals with comparable S_ySe_(1-y) stoichiometry, by cation exchange. The crystal phase of the resulting Cd(S_ySe_(1-y)) nanocrystals was either cubic or hexagonal, depending on the phase of the starting nanocrystals. One sample of cubic Cu_(2-x)(S_ySe_(1-y)) nanocrystals, with S_(0.5)Se_(0.5) chalcogenide stoichiometry, was then evaluated as the anode material in Li-ion batteries. The nanocrystals were capable of undergoing lithiation/delithiation via a displacement/conversion reaction (Cu to Li and vice versa) in a partially reversible manner.