Volume contractible Antimony bromide electrode as negative electrode for long-lasting Li-ion batteries

Abstract

Antimony is one of the promising anode materials for lithium-ion batteries due to its high volumetric and gravimetric capacity (theoretical specific capacity 660 mAh g-1) and stable voltage window (0.87-0.91V vs Li/Li+). However, a high-volume expansion ( ∼130%) of Sb on lithiation degrades the electrochemical performance and restricts its application. In this work, a novel strategy is explored to use antimony halide (SbBr3) instead of Sb as the starting anode material. In the first step, Li will react with SbBr3 to form LiBr and pure Sb, leading to a 78% contraction in volume, and then this pure Sb further lithiates to form Li3Sb expanding the volume (of the lithiated Sb by 130%). LiBr, which is a byproduct of the first reaction, dissolves into the solvent, leaving a porous Sb. In a nutshell, the two-step lithiation process results in a net volume-contacted porous antimony, ideal as an electrode to counter volumetric stress in subsequent charge-discharge cycles. The electrochemical performance of this electrode is much superior when compared with the pure antimony electrode, taking advantage of initial volume reduction and porous scaffold. It achieves a high specific discharge capacity of 345 mAh g-1 at a rate of 100mAg-1 even after the end of the 100th cycle and losing only 20% of its capacity. This shows that this volume contractible technique can be successfully employed for metals and metallic alloys having drastically higher Li-storing capacities than graphite.