For electrochemical supercapacitors, nickel cobaltite (NiCo
2O
4) has emerged as a new energy storage material. The electrocapacitive performance of metal oxides is significantly influenced by their morphology and electrical characteristics. The synthesis route can modulate the morphological structure, while their energy band gaps and defects can vary the electrical properties. In addition to modifying the energy band gap, doping can improve crystal stability and refine grain size, providing much-needed surface area for high specific capacitance. This study evaluates the electrochemical performance of aluminum-doped Ni
1−xAl
xCo
2O
4 (0 ≤ x ≤ 0.8) compounds. The Ni
1−xAl
xCo
2O
4 samples were synthesized through a hydrothermal method by varying the Al to Ni molar ratio. The physical, morphological, and electrochemical properties of Ni
1−xAl
xCo
2O
4 are observed to vary with Al
3+ content. A morphological change from urchin-like spheres to nanoplate-like structures with a concomitant increase in the surface area, reaching up to 189 m
2/g for x = 0.8, was observed with increasing Al
3+ content in Ni
1−xAl
xCo
2O
4. The electrochemical performance of Ni
1−xAl
xCo
2O
4 as an electrode was assessed in a 3M KOH solution. The high specific capacitance of 512 F/g at a 2 mV/s scan rate, 268 F/g at a current density of 0.5 A/g, and energy density of 12.4 Wh/kg was observed for the x = 0.0 sample, which was reduced upon further Al
3+ substitution. The as-synthesized Ni
1−xAl
xCo
2O
4 electrode exhibited a maximum energy density of 12.4 W h kg
−1 with an outstanding high-power density of approximately 6316.6 W h kg
−1 for x = 0.0 and an energy density of 8.7 W h kg
−1 with an outstanding high-power density of approximately 6670.9 W h kg
−1 for x = 0.6. The capacitance retention of 97% and 108.52% and the Coulombic efficiency of 100% and 99.24% were observed for x = 0.0 and x = 0.8, respectively. First-principles density functional theory (DFT) calculations show that the band-gap energy of Ni
1−xAl
xCo
2O
4 remained largely invariant with the Al
3+ substitution for low Al
3+ content. Although the capacitance performance is reduced upon Al
3+ doping, overall, the Al
3+ doped Ni
1−xAl
xCo
2O
4 displayed good energy, powder density, and retention performance. Thus, Al
3+ could be a cost-effective alternative in replacing Ni with the performance trade off.
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