Morphological impact on the supercapacitive performance of nanostructured ZnO electrodes

This study investigated the influence of the ZnO morphology on the energy storage capacity of symmetric supercapacitor devices, focusing on the defect centers present in the materials due to morpho-structural differences. Thus, ZnOs with five different morphologies were synthesized with varying methods in which the nanoparticles have the form of flowers, bullets, pyramids, hexagons, and rods. All materials were thoroughly characterized by scanning/transmission electron microscopy, X-ray diffraction, and spectroscopic techniques like photoluminescence, UV-vis, Raman, and electron paramagnetic resonance spectroscopy. Subsequently, the ZnO-based materials were assembled in symmetric supercapacitor devices to test their energy storage capabilities. The ZnO with nanorod and hexagonal morphologies showed the best specific capacity (180 and 142 F/g), energy density (25 and 19 Wh/kg), and power density (211 and 252 kW/kg) values. The importance of the defect centers in the materials was highlighted, where the ratio between the Zn and O vacancies, evidenced by EPR spectroscopy, plays a crucial role in the ZnO materials’ energy storage capacity. The Raman results support the proposed model, which underlines the importance of oxygen vacancies. In contrast, BET measurements show that the specific surface area of the morphologically distinct ZnO materials does not change drastically, validating the importance of the defect centers in the materials. A so-called ”bottle-neck” effect is proposed to describe the relation between the paramagnetic vacancies and the electric properties of the materials.