Boosting Salinity Energy Extraction Efficiency in Capacitive Mixing by Polyelectrolyte Surface Coating.

The extraction of salinity gradient energy in the capacitive mixing (CapMix) technique can be enhanced by using polyelectrolyte-coated electrodes. The micromechanism of polyelectrolyte (PE) coating enhancing the salinity energy extraction is studied by using a statistical thermodynamic theory. When PE takes same charge sign as the coated electrodes, the extraction efficiency can be boosted owing to the enhanced response of electrical double layer (EDL) to external cell voltage (V0). For the optimal case studied, the extraction efficiency was boosted from 0.25 to 1.25% by PE coatings. Owing to counterion adsorption and the enhanced response of EDL, the extraction energy density presented a local maximum at V0 = 0, which is higher than another local maximum value when V0 ≠ 0. This provides important guidance on the two approaches of CapMix in terms of capacitive Donnan potential (CDP, V0 = 0) and capacitive double-layer expansion (CDLE, V0 ≠ 0). Under the effects of PE coating, the extraction efficiency by CDLE can be improved to about 11% by CDP for the optimal studied case. The synergistic effect of grafting conditions can significantly elevate the energy density and extraction efficiency of the CDP process.

Effects of Kinetic Dielectric Decrement on Ion Diffusion and Capacitance in Electrochemical Systems.

Diffusion of ionic components in electrolytes not only eliminates the gradients of ionic concentrations but also alters the local dielectric environment, and the coupling effect between kinetic dielectric decrement and ionic concentration gradient on the diffusion dynamics is not well understood. Herein, taking the charging process in electrical double layer systems as a case study, we conduct a multiscale investigation of ion diffusions in aqueous electrolytes by combining the dynamic density functional theory and an ion-concentration-dependent dielectric constant model. By properly considering the time evolutions of local dielectric constant coupled with ion density, we report an interesting phenomenon on the suppression of surface charge density that is not captured by conventional models. In addition, we show that the usage of aqueous electrolyte with small dielectric decrement coefficients promotes the capacitance, in quantitative agreement with experimental measurements.