Abstract
Geometrically well-defined Cu6Sn5 thin films were used as model systems to estimate the diffusion depth and diffusion pathway requirements of Li and Na ions in alloy anodes. eta-Cu6Sn5 anodes have an initial reversible capacity towards Li of 545 mAh g-1 (Li3.96Sn or 19.8 Li/Cu6Sn5) and a very low initial irreversible capacity of 1.6 Li/Cu6Sn5. In contrast, the reaction with Na is limited with a reversible capacity of 160 mAh g-1 compared to the expected 516 mAh g-1. The potential profile is analogous to that of pure Sn with an average potential of 0.3 V. X-ray diffraction and 119Sn-Mössbauer measurements show that this limited capacity is likely resulting from the limited diffusion of Na into the anode particles not the formation of a low Na-content phase. This is substantiated by the analysis of the structure of eta-Cu6Sn5 which revealed zig-zag and tunnel diffusion pathways with spherical voids with a diameter very close to that of Na+. Moreover, our results also indicate that an alloy of eta-Cu6Sn5 should have optimized particle sizes of about 10 nm in diameter to increase the Na-capacity significantly. An alternative system consisting of a mixture of Cu6Sn5 and Sn of nominal composition ‘Cu6Sn10’ has been studied as possible Na-ion anode material possessing higher storage capacity than pure Cu6Sn5. Indeed this mixture of phase delivers a larger initial reversible storage capacity up to 400 mAh g-1. Finally, we have evidenced that the presence of Cu in Cu6Sn5 and in ‘Cu6Sn10’ suppresses the anomalous electrolyte decomposition normally measured for pure Sn at 1.2 V during discharge.
