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Two kinds of electrode materials were produced to fabricate asymmetric supercapacitor devices (i) Highly defective, n-type wide bandgap semiconductor ZnO nanocrystalline electrodes below 50 nm were synthesized with the aid of the high energy ball milling technique. (ii) Flexible 3D-graphene foams were synthesized via the chemical vapor deposition technique. Extensive defect structure analysis was performed via enhanced characterization techniques mainly the spectroscopy ones electron paramagnetic resonance (EPR), Raman, and photolumine