Abstract

Nanostructured metal oxides (NMOs) have emerged as promising candidates for high-performance supercapacitors owing to their rich redox activity, high surface area, and structural versatility. This chapter provides a computationally guided overview of NMOs for supercapacitor applications, emphasizing how Density Functional Theory (DFT) and complementary theoretical tools accelerate material discovery and optimization. We systematically explore three core computational approaches band structure and DOS analysis, adsorption energy calculations, and surface diffusion barrier estimations via the Nudged Elastic Band (NEB) method to reveal their predictive value in tuning conductivity, ion surface interactions, and charge transport properties. Case studies demonstrate that NMOs such as NiCo₂O₄ achieve specific capacitances exceeding 900 F g⁻¹, while NiMoO₄ delivers 168.9 mAh g⁻¹ with 80% retention after 7000 cycles. DFT calculations closely match experimental results for NiMoO₄ [110] (predicted 203 mAh g⁻¹), validating computational accuracy. Band structure and DOS analysis highlights the role of high DOS near the Fermi level in enhancing conductivity, with sulfide analogues (e.g., Co₃S₄, NiCo₂S₄) outperforming oxides due to reduced band gaps. Adsorption energy studies reveal optimal ion binding sites and the influence of defects, dopants, and surface terminations on stability and capacitance. NEB-based diffusion studies quantify migration barriers, showing that vacancy engineering and morphology control can significantly enhance ion mobility. This chapter concludes that the synergy between nanostructure engineering and computational modeling provides a robust pathway toward the development of commercially viable, scalable, and sustainable supercapacitors.