Interfacial microstructure of neutral and charged polymer brushes: A density functional theory study.

Polymer density functional theory (PDFT) is a computationally efficient and robust statistical mechanics theory for capturing the interfacial microstructure of grafted polymer brushes (PBs). Undoubtedly, the intramolecular and intermolecular interactions in PDFT (e.g., hard-core interactions and direct Coulomb interactions) are greatly affected by the grafting behavior of PBs. However, the combination of these interactions with the physical constraints on grafting behavior remains unclear and there is a remarkable difference in the density profile of grafted PB between PDFT and simulation. Herein, we propose a PDFT to study neutral and charged grafted PBs by incorporating the physical constraints of end-grafted PBs into the excess free energies due to intramolecular and intermolecular interactions. This PDFT has been successfully validated where the density distributions of neutral and weakly charged PBs predicted by the PDFT are in excellent agreement with the results of the Monte Carlo and molecular dynamics simulations. In addition, the significant contribution of grafting behavior to the free energy of PB systems is presented. Consequently, this work provides a powerful and accurate theoretical method to reveal the interfacial microstructure of grafted PBs.

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.

Wetting Transition of Ionic Substrate by Modulating Surface Charge Distribution.

Surface wettability regulation plays a crucial role in antifouling and related applications. For regulating surface wettability, one of the effective approaches is to modulate the surface charge distribution. Herein, we report a theoretical study for unraveling the mechanistic relation between surface charge distribution and ionic substrate wettability. Specifically, acetonitrile liquids at ambient condition in contact with various ionic substrates are considered. At different surface charge distributions, the interfacial thermodynamic properties are investigated by means of molecular density functional theory. We find that the variation of the spatial interval among the discrete charges strongly alters the substrate-acetonitrile interaction and leads to an oscillation in the interfacial tension, indicating that the substrate can be tuned from a solvophobic one to a solvophilic one. This trend can be further enhanced by increasing the charge quantity. The underlying mechanisms are extensively discussed and expatiated. Our work provides theoretical guidance to engineer and regulate surface wettability.

Dynamic Adsorption of Ions into Like-Charged Nanospace: A Dynamic Density Functional Theory Study.

The adsorption processes of ions into charged nanospace are associated with many practical applications. Whereas a large number of microporous materials have been prepared toward efficient adsorption of ions from solutions, theoretical models that allow for capturing the characteristics of ion dynamic adsorption into like-charged nanopores are still few. The difficulty originates from the overlapping of electric potentials inside the pores. Herein, a theoretical model is proposed by incorporating dynamic density functional theory with modified Poisson equation for investigating the dynamic adsorption of ions into like-charged nanoslits. This model is rationalized by comparing the theoretical predictions with corresponding simulation results. Afterward, by analyzing the adsorption dynamics, we show that the overlapping effect is associated with the pore size, ion bulk concentration, and surface charge density, and it plays a dominant role in the coupling between the total adsorption amount of ions and total adsorption time. Specifically, with weak overlapping effect, the total adsorption amount is intuitively proportional to the total adsorption time; however, when the overlapping effect is strong, the total adsorption amount may be inversely proportional to the total adsorption time, indicating that both high adsorption amount and short adsorption time can be achieved simultaneously. This work provides a meaningful insight toward the rational design and optimization of microporous materials for efficient ion adsorption.

Enabling High-Capacitance Supercapacitors by Polyelectrolyte Brushes.

Polyelectrolyte brushes (PEBs) hold excellent potential for designing high-capacitance electrical double-layer capacitors (EDLCs), a crucial component of supercapacitors. Both experiments and computational simulations have shown their energy-storage advantage. However, the effect of PEBs on the energy storage of EDLCs is not yet fully understood. Herein, we systematically study the energy-storage effects of polyanionic (PA) and polycationic (PC) brushes using polymer density functional theory (DFT). First, the application of polymer DFT in polyelectrolyte-grafted EDLCs is successfully validated using molecular dynamics simulations. With the help of polymer DFT, an interfacial adhesion microstructure of the PA/PC brushes is observed. Most importantly, the results show that polyelectrolyte-grafted EDLCs achieve a significant increase in capacitance at low salt concentrations and surface voltages, offering an excellent energy-storage advantage over traditional EDLCs. However, this advantage is considerably diminished at high salt concentrations or surface voltages, showing unusual salt- and voltage-dependent behaviors of energy-storage capacity. Nonetheless, the PC-grafted EDLCs maintain their outstanding energy-storage performance, even at relatively high salt concentrations and surface voltages. These findings deepen our comprehension of PEBs at the molecular level and provide insights for the molecular design of high-capacitance supercapacitors.

Long-Lived Weak Ion Pairs in Ionic Liquids: An Insight from All-Atom Molecular Dynamics Simulations.

The microstructure and local dynamics of ions in room-temperature ionic liquids (RTILs) have drawn a lot of attention due to their extensive potential applications in numerous fields. It is well-known that the widely used definitions of ion pairs (IPs) cannot reflect the full picture of RTILs. In this study, we find a universal residence time (τMR), which is regardless of the number of counterions in the first solvation shell in RTILs. Inspired by this, we propose a weak IP (WIP) model from a spatiotemporal perspective and demonstrate that the WIPs are long-lived and that their lifetimes obey a log-normal distribution, which is different from the literature. In addition, the electrostatic interactions are the main factors in the formation of WIPs, and the reorientations of ions are vital to the ruptures of WIPs. This research provides a new perspective for understanding the microstructural and dynamical properties of RTILs.

Double-Edged Sword of Ion-Size Asymmetry in Energy Storage of Supercapacitors.

The advanced supercapacitor is of great significance for renewable energy storage. Achieving its high energy and high power densities remains a huge challenge. Herein, the contribution of ion-size asymmetry to the charging behavior of a supercapacitor is systematically studied using time-dependent density functional theory (TDDFT). We track the time evolution of the ionic microstructure inside the porous electrode and its reservoir and reveal a kinetic charge inversion in the asymmetrical ion-size cases. Compared with the symmetrical ion-size case, we find that the ion-size asymmetry has a double-edged sword effect on the energy storage of a supercapacitor: it accelerates the charging process yet reduces the differential capacitance. Additionally, the energy density and power density can simultaneously increase in the asymmetrical cases, which provides important insights toward the experimental design of supercapacitors with high energy and high power densities.

Surface Charge Density in Electrical Double Layer Capacitors with Nanoscale Cathode-Anode Separation.

Using a dynamic density functional theory, we study the charging dynamics, the final equilibrium structure, and the energy storage in an electrical double layer capacitor with nanoscale cathode-anode separation in a slit geometry. We derive a simple expression for the surface charge density that naturally separates the effects of the charge polarization due to the ions from those due to the polarization of the dielectric medium and allows a more intuitive understanding of how the ion distribution within the cell affects the surface charge density. We find that charge neutrality in the half-cell does not hold during the dynamic charging process for any cathode-anode separation, and also does not hold at the final equilibrium state for small separations. Therefore, the charge accumulation in the half-cell in general does not equal the surface charge density. The relationships between the surface charge density and the charge accumulation within the half-cell are systematically investigated by tuning the electrolyte concentration, cathode-anode separation, and applied voltage. For high electrolyte concentrations, we observe charge inversion at which the charge accumulation exceeds the surface charge at special values of the separation. In addition, we find that the energy density has a maximum at intermediate electrolyte concentrations for a high applied voltage.