Physical properties of heteroatom doped graphene monolayers in relation to supercapacitive performance

Abstract

Electrodes fabricated using graphene are quite promising for electric double layer capacitors. However graphene has the limitations of low ‘Quantum Capacitance (QC)’ near fermi level due to the presence of Dirac point that can be modified by doping graphenewith suitable dopant. The density functional theory DFT calculations are performed for doped graphene using Boron, Sulphur and phosphorus as dopants to improve the quantum capacitance of electrodes fabricated using graphene. The calculations are performed at temperatures of 233, 300 and 353 °K. From present calculations no significant temperature dependence of quantum capacitance is observed, however a marked increase in QC of value above 58μFcm^-2 is seen. Forphosphorus and Sulphur doped graphene a significant energy gap shift of ~ 1.5 eV from the Fermi level is observed that significantly increases the QC at Fermi level to a high value of ~ 35 μFcm^-2. With boron dopant as well, a shift of energy gap ~ 1.25eV from the Fermi level is observed. The shift in Dirac point increases quantum capacitance at Fermi level that in turn can increase the energy density of supercapacitor remarkably. The effect of increasing doping concentration on quantum capacitance is also investigated. These results suggest that doping of graphene may result in significant increase in QC near Fermi level, if the dopants are selected carefully depending upon the use of graphene as a positive or negative electrode. The results of these calculations reveal that the problem of low QC of graphene in the range of interest can be addressed by modifying itssurface and structure chemistry which may increase energy density in supercapacitors.