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Megh Dutta

Publications and source records attributed to Megh Dutta.

3 recordsLinked to original sources

Accelerating charging dynamics of electric double-layer capacitors

Electric double-layer capacitors (EDLCs), consisting of an ionic fluid between two metallic electrodes, are electrochemical energy storage devices complementary to batteries, allowing for a faster charge/discharge. The charging dynamics in response to a voltage step features a variety of regimes and relaxation timescales, depending on the applied voltage and the various lengths characterizing the system, most importantly the inter-electrode distance and the Debye length over which electrostatic effects are screened in the electrolyte. Inspired by recent works on "shortcut to adiabaticity" in colloidal systems, here we investigate the possibility to control the charge and discharge of planar EDLCs using time-dependent voltages. Specifically, our aim is to achieve a full charge or discharge within a finite time shorter than their intrinsic relaxation timescales. Within the Poisson-Nernst-Planck model and the small-voltage regime, we derive time-dependent protocols that can eliminate an arbitrary number of relaxation modes. This permits to approach the equilibrium charged state within a finite time, that can be in practice an order of magnitude faster than the natural equilibration time. We illustrate the relevance and efficacy of the method on polynomial drivings and show that the surface charge density, charge-density profiles, and global deviation from equilibrium (quantified by a Kullback-Leibler-like divergence) can all be significantly accelerated, even for driving times comparable to or shorter than the natural RC time of the system.

cond-mat.soft

Poisson-Nernst-Planck charging dynamics of an electric double layer capacitor: symmetric and asymmetric binary electrolytes

A parallel plate capacitor containing an electrolytic solution is the simplest model of a supercapacitor, or electric double layer capacitor. Using both analytical and numerical techniques, we solve the Poisson-Nernst-Planck equations for such a system, describing the mean-field charging dynamics of the capacitor, when a constant potential difference is abruptly applied to its plates. Working at constant total number of ions, we focus on the physical processes involved in the relaxation and, whenever possible, give its functional shape and exact time constants. We first review and study the case of a symmetric binary electrolyte, where we assume the two ionic species to have the same charges and diffusivities. We then relax these assumptions and present results for a generic strong (i.e. fully dissociated) binary electrolyte. At low electrolyte concentration, the relaxation is simple to understand, as the dynamics of positive and negative ions appear decoupled. At higher electrolyte concentration, we distinguish several regimes. In the linear regime (low voltages), relaxation is multi-exponential, it starts by the build-up of the equilibrium charge profile and continues with neutral mass diffusion, and the relevant time scales feature both the average and the Nernst-Hartley diffusion coefficients. In the purely nonlinear regime (intermediate voltages), the initial relaxation is slowed down exponentially due to increased capacitance, while bulk effects become more and more evident. In the fully nonlinear regime (high voltages), the dynamics of charge and mass are completely entangled and, asymptotically, the relaxation is linear in time. We finally discuss non-ideal behavior in real capacitors and provide conditions for which mean-field is expected to hold.

cond-mat.soft

Charging dynamics of electric double layer nanocapacitors in mean-field

An electric double layer capacitor (EDLC) stores energy by modulating the spatial distribution of ions in the electrolytic solution that it contains. We determine the mean-field time scales for planar EDLC relaxation to equilibrium, after a potential difference is applied. We tackle first the fully symmetric case, where positive and negative ionic species have same valence and diffusivity, and then the general, more complex, asymmetric case. Depending on applied voltage and salt concentration, different regimes appear, revealing a remarkably rich phenomenology relevant for nanocapacitors.

physics.chem-ph