Unlocking Rapid and Robust Sodium Storage Performance of Zinc-Based Sulfide <i>via</i> Indium Incorporation.

Abstract

Zinc sulfide (ZnS) exhibits promise in sodium-ion batteries (SIBs) because of its low operation voltage and high theoretical specific capacity. However, pristine ZnS is not adequate in realizing rapid and robust sodium storage owing to its low reversibility, poor structure stability, and sluggish kinetics. To date, most efforts focus on utilizing carbonaceous incorporation to improve its electrochemical performances. Nevertheless, it remains an arduous challenge for realizing superior rate capability while obtaining stable cycling. Herein, inspired by the crystal structure of hexagonal ZnIn₂S₄, which possesses an intrinsic layered feature with larger unit-cell volume versus that of ZnS, indium incorporation is thus deployed as an immediate remedy. <i>In/ex situ</i> investigations combined with density functional theory calculations are conducted to reveal the superior kinetics, high reversibility, and good structure stability of ZnIn₂S₄. Notably, the formed indium-based derivatives during cycling manifest a Na⁺ (de)intercalation process, thereby exciting a synergetic mechanism to stabilize electrochemical cycling. As a result, the electrochemical performances of Zn-based sulfide are significantly improved via the indium incorporation. Furthermore, a full cell based on the ZnIn₂S₄ anode with the superior electrochemical performance is developed. This work provides an effective tactic of heteroatom incorporation for optimizing structure as well as exciting a complementary reaction process toward developing superior anodes for high-performance alkali-ion batteries.