Theoretical investigation of quantum capacitance of Co-doped α-MnO for supercapacitor applications using density functional theory

The rapid depletion of fossil fuels and ever-growing energy demand have led to a search for renewable clean energy sources. The storage of renewable energy calls for immediate attention to the fabrication of efficient energy storage devices like supercapacitors (SCs). As an electrode material for SCs, MnO 2 has gained wide research interest because of its high theoretical capacitance, variable oxidation state, vast abundance, and low cost. However, the low electric conductivity of MnO 2 limits its practical application. The conductivity of MnO 2 can be enhanced by tuning the electronic states through substitution doping with cobalt. In the present work, first principles analysis based on density functional theory (DFT) has been used to examine the quantum capacitance ( C QC ) and surface charge ( Q ) of Co-doped MnO 2 . Doping enhanced the structural stability, electrical conductivity, potential window, and quantum capacitance of α-MnO 2 . The shortened band gap and localized states near the Fermi level improve the C QC of α-MnO 2 . For the narrow potential range (−0.4 to 0.4 V), the C QC is observed to increase with doping concentration. The highest C QC value at +0.4 V is observed to be 2412.59 μF cm −2 for Mn 6 Co 2 O 16 (25% doping), five times higher than that of pristine MnO 2 (471.18 μF cm −2 ). Mn 6 Co 2 O 16 also exhibits better C QC and ' Q ' at higher positive bias. Hence, it can be used as an anode material for asymmetric supercapacitors. All these results suggest better capacitive performance of Co-doped α-MnO 2 for aqueous SCs and as an anode material for asymmetric supercapacitors. Substitution doping of cobalt in α-MnO 2 can enhance its structural stability, electric conductivity, potential window, and surface charge density. The shortened band gap and localized states near the Fermi level improve the quantum capacitance ( C QC ) of α-MnO 2 .