Theoretical investigation of quantum capacitance of Co-doped α-MnO2 for supercapacitor applications using density functional theory

Ariya K Vijayan; Sreehari M S; Simran Kour; Saptarshi Ghosh Dastider; Krishnakanta Mondal; A L Sharma

doi:10.1039/d3cp03080f

Theoretical investigation of quantum capacitance of Co-doped α-MnO₂ for supercapacitor applications using density functional theory

Phys Chem Chem Phys. 2023 Sep 27;25(37):25789-25802. doi: 10.1039/d3cp03080f.

Authors

Ariya K Vijayan¹, Sreehari M S¹, Simran Kour¹, Saptarshi Ghosh Dastider^{1

2}, Krishnakanta Mondal³, A L Sharma¹

Affiliations

¹ Department of Physics, Central University of Punjab, Bathinda, Punjab, India, 151401. alsharma@cup.edu.in.
² Department of Chemistry, Central University of Punjab, Bathinda, Punjab, India, 151401.
³ Department of Physics & Astrophysics, University of Delhi, India, 110007.

PMID: 37724421
DOI: 10.1039/d3cp03080f

Abstract

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, MnO₂ 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 MnO₂ limits its practical application. The conductivity of MnO₂ 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 MnO₂. Doping enhanced the structural stability, electrical conductivity, potential window, and quantum capacitance of α-MnO₂. The shortened band gap and localized states near the Fermi level improve the C_QC of α-MnO₂. 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 Mn₆Co₂O₁₆ (25% doping), five times higher than that of pristine MnO₂ (471.18 μF cm^-2). Mn₆Co₂O₁₆ 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-MnO₂ for aqueous SCs and as an anode material for asymmetric supercapacitors.