Promoting Robust and Rapid Na‐Ion Storage of Molybdenum‐Based Sulfide via Rational Hetero and Hollow Structure Design

Abstract Molybdenum disulfide (MoS₂), characterized by its two‐dimensional structure and high theoretical specific capacity, is considered a prospective anode of Na‐ion battery. However, the cycling and rate capabilities are hampered by its sluggish charge transfer kinetics and poor structural stability. To overcome the issues, most efforts have been focused on optimizing the structure of MoS₂. Nevertheless, rationally designing a structure that can present rapid and durable Na‐ion storage while ensuring large charge storage remains challenges. Herein, a MoS₂/MnS heterostructure featuring a sphere‐like hollow morphology is rationally designed according to Ostwald ripening process and Kirkendall effect. This construction can effectively establish an interfacial built‐in electric field activated by MnS and MoS₂, which exhibit P‐type and N‐type semiconductor characteristics, respectively, thereby promoting electrochemical kinetics. Moreover, excellent structural stability of MoS₂/MnS after repeated (de)sodiation processes is remarkably achieved thanks to the robust morphology design, significantly achieving outstanding tolerance to structural changes. Consequently, the MoS₂/MnS anode delivers high specific capacity (594.8 mAh g⁻¹ at 0.1 A g⁻¹), superior rate performance (up to 100 A g⁻¹), and ultrastable cycling capability (30 000 cycles with ≈81.4% retention). The work affords an effective structural optimization tactic to rationally develop high‐performance conversion‐type electrodes for alkali‐ion batteries.