Self-templated hollow nanospheres of B-site engineered non-stoichiometric perovskite for supercapacitive energy storage via anion-intercalation mechanism

J Colloid Interface Sci. 2021 Oct 15:600:729-739. doi: 10.1016/j.jcis.2021.03.147. Epub 2021 Mar 29.

Abstract

The continual increase in energy demand and inconsistent supply have attracted attention towards sustainable energy storage/conversion devices, such as electrochemical capacitors with high energy densities and power densities. Perovskite oxides have received significant attention as anion-intercalation electrode materials for electrochemical capacitors. In this study, hollow nanospheres of non-stoichiometric cubic perovskite fluorides, KNi1-xCoxF3-δ (x = 0.2; δ = 0.33) (KNCF-0.2) have been synthesized using a localized Ostwald ripening. The electrochemical performance of the non-stoichiometric perovskite has been studied in an aqueous 3 M KOH electrolyte to categorically investigate the fluorine-vacancy-mediated charge storage capabilities. High capacities up to 198.55 mA h g-1 or 714.8 C g-1 (equivalent to 1435 F g-1) have been obtained through oxygen anion-intercalation mechanism (peroxide pathway, O-). The results have been validated using ICP (inductively coupled plasma mass spectrometry) analysis and cyclic voltammetry. An asymmetric supercapacitor device has been fabricated by coupling KNCF-0.2 with activated carbon to deliver a high energy density of 40 W h kg-1 as well as excellent cycling stability of 98% for 10,000 cycles. The special attributes of hollow-spherical, non-stoichiometric perovskite (KNCF-0.2) have exhibited immense promise for their usability as anion-intercalation type electrodes in supercapacitors.

Keywords: Anion-intercalation; Hollow nanospheres; Non-stoichiometric perovskite; Ostwald ripening; Peroxide pathway; Supercapacitor.