Raman probing carbon & aqueous electrolytes interfaces and molecular dynamics simulations towards understanding electrochemical properties under polarization conditions in supercapacitors

R Vicentini and LM Da Silva and DV Franco and WG Nunes and J Fiates and G Doubek and LFM Franco and RG Freitas and C Fantini and H Zanin, JOURNAL OF ENERGY CHEMISTRY, 60, 279-292 (2021).

DOI: 10.1016/j.jechem.2021.01.003

Raman probing of carbon electrode and electrolyte under dynamic conditions is performed here using different aqueous electrolytes to elucidate the fundamental events occurring in electrochemical supercapacitor during charge-discharge processes. The areal capacitance ranges from 1.54 to 2.31 mF cm(-2) and it is determined using different techniques. These findings indicate that the Helmholtz capacitance governs the overall charge-storage process instead of the space charge (quantum) capacitance commonly verified for HOPG electrodes in the range of similar to 3 to 7 mu F cm(-2). Molecular dynamics simulations are employed to elucidate the origin of the reversible Raman spectral changes during the charge-discharge processes. A correlation is verified between the reversible Raman shift and the surface excesses of the different ionic species. A theoretical framework is presented to relate the effect of the applied potential on the Raman shift and its correlation with the surface ionic charge. It is proposed that the Raman shift is governed by the interaction of solvated cations with graphite promoted by polarization conditions. It is the first time that a comparative study on different aqueous electrolyte pH and cation ion size has been performed tracking the Raman spectra change under dynamic polarization conditions and contrasting with comprehensive electrochemistry and dynamic molecular simulations studies. This study shines lights onto the charge-storage mechanism with evidence of Kohn anomaly reduction in the carbon electrode during the reversible adsorption/desorption and insertion/extraction of ionic species. (C) 2021 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.

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