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.