摘要
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 2.31μF cm^(-2)μm 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~3 to 7μF 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 p H 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.
基金
the financial support from the Brazilian funding agencies CNPq(301486/2016-6)
the FAEPEX(2426/17),the FAPESP(2016/25082-8,2017/11958-1,2014/02163-7,2018/20756-6,2018/02713-8)and CAPES(1740195)
the‘‘Funda??o ao AmparoàPesquisa do Estado de Minas Gerais-FAPEMIG”(Project CEX112-10)
the‘‘Secretaria de Estado de Ciência,Tecnologia e Ensino Superior de Minas Gerais-SECTES/MG”(Support for the LMMA Laboratory)
the‘‘Conselho Nacional de Desenvolvimento Científico e Tecnológico–CNPq”(PQ-2 grant)
support Shell and the strategic importance of the support given by ANP(Brazil’s National Oil,Natural Gas and Biofuels Agency)through the R&D levy regulation
the Center for Research Computing(CRC)at the University of Notre Dame for the computational resources,and the Brazilian agencies CNPq(Reference Number 203393/2018-0)and CAPES(Finance Code 001)for the financial support
financial support from the FAPEMIG,CNPq(307742/2017-2 and 432384/2018-9)
Brazilian Institute of Science and Technology in Carbon Nanomaterials(INCTNanocarbono)。
