Low temperature scalable synthetic approach enabling high bifunctional electrocatalytic performance of NiCo2S4 and CuCo2S4 thiospinels.

ABSTRACT

Ternary metal sulfides are currently in the spotlight as promising electroactive materials for high-performance energy storage and/or conversion technologies. Extensive research on metal sulfides has indicated that, amongst other factors, the electrochemical properties of the materials are strongly influenced by the synthetic protocol employed. Herein, we report the electrochemical performance of uncapped NiCo2S4 and CuCo2S4 ternary systems prepared via solventless thermolysis of the respective metal ethyl xanthate precursors at 200 and 300 °C. The structural, morphological and compositional properties of the synthesized nanoparticles were examined by powder X-ray diffraction (p-XRD), transmission electron microscopy (TEM), high-resolution TEM, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and energy-dispersive X-ray spectroscopy (EDX) techniques. Electrochemical studies indicate that NiCo2S4 nanoparticles synthesized at 300 °C exhibit superior energy storage characteristics with a high specific capacitance of ca. 2650 F g-1 at 1 mV s-1, as compared to CuCo2S4 nanoparticles, which showcased a specific capacitance of ca. 1700 F g-1 at the same scan rate. At a current density of 0.5 A g-1, NiCo2S4 and CuCo2S4 nanoparticles displayed specific capacitances of 1201 and 475 F g-1, respectively. In contrast, CuCo2S4 nanoparticles presented a higher electrocatalytic activity with low overpotentials of 269 mV for oxygen evolution reaction (OER), and 224 mV for the hydrogen evolution reaction (HER), at 10 mA cm-2. The stability of the catalysts was examined for 2000 cycles in which a negligible change in both OER and HER activities was observed.