Nanometer-scale Sn coatings improve the performance of silicon nanowire LIB anodes

Abstract

We demonstrate that a thin partially dewetted coating of Sn will improve the cycling performance of silicon nanowire (SiNWs) lithium ion battery (LIB) anodes. The optimum architecture 3Sn/SiNWs (i.e. a Sn layer with an average film thickness of a 3 nm covering the nanowire) maintained a reversible capacity of 1865 mA h g⁻¹ after 100 cycles at a rate of 0.1 C. This is almost double of the baseline uncoated SiNWs, where the reversible capacity after 100 cycles was 1046 mA h g⁻¹ (∼78% improvement). The 1Sn/SiNWs and 3Sn/SiNWs electrodes demonstrated much improved cycling coulombic efficiency, with >99% vs. 94–98% for the baseline. At a high current density of 5 C, these nanocomposite offered 2× the capacity retention of bare SiNWs (∼20 vs. ∼10% of 0.1 C capacity). It is demonstrated that the Sn coating both lithiates and delithiates at a higher voltage than Si and thus imparts a compressive stress around the nanowires. This confines their radial expansion in favor of longitudinal, and reduces the well-known failure mode by lithiation-induced nanowire stranding and fracture. TOF-SIMS analysis on the post-cycled delithiated specimens shows enhanced Li signal near the current collector due to accelerated SEI formation at the interface. FIB demonstrates concurrent en-masse delamination of SEI agglomerated sections of the nanowires from the current collector. Both of these deleterious effects are lessened by the presence of the Sn coatings.