2025/03/19 by Fertig, David, Janssen, Mathijs · 1 citation
#Chemical Physics (physics.chem-ph) #FOS: Physical sciences #Soft Condensed Matter (cond-mat.soft)
paper · doi:10.48550/arxiv.2503.15171
Electric double layer (EDL) formation underlies the functioning of supercapacitors and several other electrochemical technologies. Here, we study how the EDL formation near two flat blocking electrodes separated by 2L is affected by beyond-mean-field Coulombic interactions, which can be substantial for electrolytes of high salt concentration or with multivalent ions. Our model combines the Nernst-Planck and Bazant-Storey-Kornyshev (BSK) equations; the latter is a modified Poisson equation with a correlation length ℓc. In response to a voltage step, the system charges exponentially with a characteristic timescale τ that depends nonmonotonically on ℓc. For small ℓc, τ is given by the BSK capacitance times a dilute electrolyte's resistance, in line with [Zhao, Phys. Rev. E 84, 051504 (2011)]; here, τ decreases with increasing ℓc. Increasing the correlation length beyond ℓc≈ L2/3λD1/3, with λD the Debye length, τ reaches a minimum, rises as τ∝ λDℓc/D, and plateaus at τ=4L2/(π2 D). Our results imply that strongly correlated, strongly confined electrolytes - ionic liquids in the surface force balance apparatus, say - move slower than predicted so far.