Pseudocapacitors are energy-storage devices characterized by fast and reversible redox reactions that enable them to store large amounts of electrical energy at high rates. We simulate the response of pseudocapacitive electrodes under realistic conditions to identify the microscopic factors that determine their performance, focusing on ruthenia (RuO2) as a prototypical electrode material. Electronic-structure methods are used together with a self-consistent continuum solvation (SCCS) model to build a complete dataset of free energies as the surface of the charged electrode is gradually covered with protons under applied voltage. The resulting dataset is exploited to compute hydrogenadsorption isotherms and charge-voltage responses by means of grand-canonical sampling, finding close agreement with experimental voltammetry. These simulations reveal that small changes on the order of 5 µF/cm 2 in the intrinsic double-layer capacitance of the electrode-electrolyte interface can induce variations of up to 40 µF/cm 2 in the overall pseudocapacitance.
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