Asymmetric electrostatic properties of an electric double layer: a generalized Poisson-Boltzmann approach taking into account non-uniform size effects and water polarization

Asymmetric size of ions and orientational ordering of water dipoles in electric double layer model - an analytical mean-field approach

“…The latter was already studied within an approximate approach for small volume shares of ions everywhere in the electrolyte solution, where the number densities of ions and water molecules were obtained implicitly [52]. In contrast, here the number densities of ions and water molecules are given explicitly by analytic expressions (Eqs.…”

“…The model can be also used to study the cell membrane interactions with different biomaterials/implants or interaction of cells with inorganic nanoparticles and nanostructured surfaces [14]. In colloid science [22] and electrochemistry [1,24], the presented model can be used in the studies of electrode/ionic liquids interface, as for example in calculation of differential capacitance [10,12,14,24,48,52] (Fig.4) where the metallic or semiconductor electrodes are in contact with different kind of electrolytes having asymmetric size of ions [51]. Finally, hybrid nanoporous semiconductor electrodes [57], covered by organic materials, are gaining more and more interest, as for example in construction of supercapacitors [58].…”

Effect of proximity to ionic liquid-solvent demixing on electrical double layers

“…In Eqs. (8) and (9), the cations and anions are assumed to be of the same size, i.e., a − = a + = a, whereas often a + = a − [44][45][46]. Gongadze and Iglič [44] proposed an improved mean-field model of EDLs that accounts for such ion-size asymmetry, and found that it leads to a pronounced decrease of the capacitance and to shape asymmetry of the capacitancevoltage curves (with respect to the potential of zero charge), which seems to be consistent with the experimental observations [47,48].…”

Asymmetric Finite Size of Ions and Orientational Ordering of Water in Electric Double Layer Theory Within Lattice Model

“…Therefore, it seems appropriate to give to Eq. 20 We took into account the orientational ordering of water and asymmetric finite size of ions in the prediction of an asymmetric camel-like (saddle-like) shape of the voltage dependence of the differential capacitance [45,46] (Fig. 5).…”

“…The decrement of the relative permittivity in the electrolyte solution near the charged surface is influenced also by the excluded volume effect due to the competition between counterions and water molecules [35]. To consider different size of positive and negative ions, the generalisation of GI model [34] was first performed by Sin et al [45], assuming small volume shares of ions everywhere in electrolyte solution only, where the number densities of ions and water molecules were obtained implicitly.…”