Unveiling the role of dopants in boosting CuS supercapacitor performance: insights from first-principles calculations

Transition metal sulfides have become famous in high energy density supercapacitor materials owing to their rich redox and high conductivity. While their development has achieved a breakthrough in terms of capacitance, there is little knowledge from the theoretical perspective on how dopants play a role in enhancing their capacitances. In this work, pseudocapacitance and quantum capacitance were evaluated through first-principles calculation to describe their role in transition metal sulfide, which here is represented by copper sulfide (CuS). The resulting quantum capacitance (C_Q) was calculated in both the bulk and surface of CuS to determine which structure has a greater effect on the capacitance of the system. It was observed that the dopant increased C_Q in the bulk system, which is different from the C_Q of surface structures. Meanwhile, K⁺ ions were introduced on the surface structure to calculate transfer charge and work function shift, thus determining pseudocapacitance. All dopant types were able to increase the pseudocapacitance value, with Fe doping showing the highest capacitance of 111 F g^-1, which is higher than that of the pristine structure (47 F g^-1). The role of the dopant is discussed in detail in this work. Our results suggest that the increased capacitance of doped TMS materials was originated not only from the geometrical perspective but also from the higher pseudocapacitance value. Quantum capacitance, alternatively, could also contribute to the system when the dopant occurs in the bulk rather than only in the surface structure. This work may open a new perspective on how dopants play a role in increasing supercapacitor performance.