Sulfur Vacancies‐Engineered Ni3S4‐x Hollow Microspheres with Optimized Anionic Adsorption Energy for High‐Performance Supercapacitor

Abstract Nickel sulfides with high theoretical capacitance have aroused tremendous attention for next‐generation supercapacitors. Unfortunately, the structural durability of nickel sulfides is insufficient to support the long‐term working situation. Herein, Ni 3 S 4‐x hollow microspheres with sulfur vacancies (Ni 3 S 4‐x HMs) are constructed by a liquid‐phase anion exchange process using the Ni‐MOF as the precursor. Both experimental investigation and theoretical analysis suggest that the deliberately introduced sulfur vacancies effectively improve the anionic adsorptive ability of nickel sulfides in the KOH electrolyte, significantly enhancing the reversible capacitance and structural durability (1884 F g ‐1 at 2 A g ‐1 , capacity retention of 97.9% after 10 000 cycles). In addition, an asymmetrical solid‐state supercapacitor consisting of Ni 3 S 4‐x HMs cathode and activated carbon anode shows infusive energy/power density (33.05 Wh kg ‐1 /1.68 kW kg ‐1 ) and remains 82.4% over 10 000 repeated charging/discharging processes in the KOH‐PVA gel electrolyte. The strategies can be developed to enlighten the structural design of various metal sulfides materials adopted in electrochemical energy storage devices including alkali ion batteries, supercapacitors, and electrocatalysts.