Concentrated aqueous solutions of multivalent macroions enhance the electrical double layer capacitance and differential capacitance of a planar supercapacitor

Abstract

The electrostatic properties of the ionic cloud, or electrical double layer, neutralizing a charged electrode are relevant to improve the storage of electrical energy and the efficiency of supercapacitors and/or batteries using coulombic fluids. In this work, we study the microscopic profiles of charged particles, integrated surface charge density, and the mean electrostatic potential associated to a pair of infinite parallel plates uncharged or, else, with opposite charge, in the presence of a salt-free aqueous solution constituted by big positive macroions and small anions, which interact via an explicit electrostatic coulombic potential and are dissolved in an implicit solvent. The particle profiles and the integrated surface charge density associated to Monte Carlo simulations and integral equations theory display an oscillatory or non-monotonic behaviour producing the phenomena of charge inversion and charge reversal. These phenomena are not predicted by the non-linear Poisson-Boltzmann equation, which highlights the importance of ion correlations and ionic volume excluded effects. The phenomenon of surface charge amplification is observed near the point of zero charge, which is yielded by the particle size-asymmetry. For a fixed concentration of macroions, a monotonic increase of the mean electrostatic potential difference between the charged parallel plates is predicted by simulations and theories as a function of the electrodes' charge. For a fixed surface charge density, the capacitance of the parallel plates capacitor increases when the ionic strength of the macroion's solution increases. A concavity inversion and an augment of the differential capacitance is also observed for an electrode near the point of zero charge as function of the macroion's concentration.