Ion‐exchange synthesis of microporous Co 3 S 4 for enhanced electrochemical energy storage

Replacing oxygen in an oxide-based material with sulfur can produce improved flexibility and more efficient electron transport in its structure leading to enhanced electrical performance. Herein, facile template-free growth of free-standing cobalt (II, III) oxide (Co3O4) on Ni foam via a mild hydrothermal technique followed by its transformation to cobalt (II, III) sulfide (Co3S4) via an ion-exchange is reported. The microstructural morphology, phase, and porosity of the prepared Co3O4 and Co3S4 are characterized by FESEM, XRD, Raman, XPS, TEM, and BET analyses. The electrochemical performance of the Co3S4 film with a microporous morphology is considerably superior to that of Co3O4, exhibiting a high specific capacitance of 1604 F g−1 (905 F g−1 for Co3O4), the excellent restorative ability of ~99% at 1 A g−1 (~96% for Co3O4), and good retention of 98% at 10 A g−1 (~70% for Co3O4). The Co3S4 electrode shows excellent capacitance endurance even after 10 000 charge/discharge cycles and a high energy density of 128.32 Wh kg−1 at 0.72 kW kg−1. A fabricated symmetric Co3S4 supercapacitor device also reveals superior charge/discharge, restorative, and retention performances compared to a Co3O4 one. The excellent supercapacitive performance of phase-transformed Co3S4 electrode is due its large electrochemically active surface area along with synergetic effect of small charge transfer resistance and high relative diffusion coefficient.