Electrochemical Properties of Multilayered Sn/TiNi Shape-Memory-Alloy Thin-Film Electrodes for High-Performance Anodes in Li-Ion Batteries.

Sn is a promising candidate anode material with a high theoretical capacity (994 mAh/g). However, the drastic structural changes of Sn particles caused by their pulverization and aggregation during charge-discharge cycling reduce their capacity over time. To overcome this, a TiNi shape memory alloy (SMA) was introduced as a buffer matrix. Sn/TiNi SMA multilayer thin films were deposited on Cu foil using a DC magnetron sputtering system. When the TiNi alloy was employed at the bottom of a Sn thin film, it did not adequately buffer the volume changes and internal stress of Sn, and stress absorption was not evident. However, an electrode with an additional top layer of room-temperature-deposition TiNi (TiNi(RT)) lost capacity much more slowly than the Sn or Sn/TiNi electrodes, retaining 50% capacity up to 40 cycles. Moreover, the charge-transfer resistance decreased from 318.1 Ω after one cycle to 246.1 Ω after twenty. The improved cycle performance indicates that the TiNi(RT) and TiNi-alloy thin films overall held the Sn thin film. The structure was changed so that Li and Sn reacted well; the stress-absorption effect was observed in the TiNi SMA thin films.