Issue 21, 2021

Charge-storage mechanism of highly defective NiO nanostructures on carbon nanofibers in electrochemical supercapacitors

Abstract

An electrode composed of highly defective nickel oxide (NiO) nanostructures supported on carbon nanofibers (CNFs) and immersed in an Li+-based aqueous electrolyte is studied using Raman spectroscopy under dynamic polarization conditions to address the charge-storage phenomenon. By this operando technique, the formation of Li2SO4·H2O during the discharge process is verified. At the same time, we observed the phase transformation of NiO to NiOOH. The Ni(OH)2/NiOOH redox couple is responsible for the pseudocapacitive behavior with intercalation of cationic species in the different Ni structures. A ‘substitutive solid-state redox reaction’ is proposed to represent the amphoteric nature of the oxide, resulting in proton intercalation, while the insertion of Li+ occurs to a less extent. The electrode material exhibits outstanding stability with 98% coulombic efficiency after 10 000 charge–discharge cycles. The excellent electrode properties can be ascribed to a synergism between CNFs and NiO, where the carbon nanostructures ensured rapid electron transport from the hydrated nickel nanoparticles. The NiO@CNF composite material is a promising candidate for future applications in aqueous-based supercapacitors. DFT simulation elucidates that compressive stress and Ni-site displacement lead to a decrease up-to 3.5-fold on the electron density map located onto the Ni-atom, which promotes NiO/Ni(OH)2/NiOOH transition.

Graphical abstract: Charge-storage mechanism of highly defective NiO nanostructures on carbon nanofibers in electrochemical supercapacitors

Supplementary files

Article information

Article type
Paper
Submitted
05 1 2021
Accepted
01 3 2021
First published
01 4 2021

Nanoscale, 2021,13, 9590-9605

Charge-storage mechanism of highly defective NiO nanostructures on carbon nanofibers in electrochemical supercapacitors

W. G. Nunes, A. N. Miranda, B. Freitas, R. Vicentini, A. C. Oliveira, G. Doubek, R. G. Freitas, L. M. Da Silva and H. Zanin, Nanoscale, 2021, 13, 9590 DOI: 10.1039/D1NR00065A

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