LAUSR

Metals such as Sb and Bi are important anode materials for sodium‐ion batteries because they feature a large capacity and low reaction potential. However, the accumulation of stress and strain upon sodium storage leads to the formation of cracks and fractures, resulting in electrode failure upon extended cycling. In this work, the design and construction of BixSb1−x bimetallic alloy films with a compositional gradient to mitigate the intrinsic structural instability is reported. In the gradient film, the top is rich in Sb, contributing to the capacity, while the bottom is rich in Bi, helping to reduce the stress in the interphase between the film and the substrate. Significantly, this gradient film affords a high reversible capacity of ≈500 mAh g−1 and sustains 82% of the initial capacity after 1000 cycles at 2 C, drastically outperforming the solid‐solution counterpart and many recently reported alloy anodes. Such a gradient design can open up the possibilities to engineering high‐capacity anode materials that are structurally unstable due to the huge volume variation upon energy storage.