Asymptotic analysis on charging dynamics for stack-electrode model of supercapacitors

Supercapacitors are promising electrochemical energy storage devices due to their prominent performance in rapid charging/discharging rates, long cycle life, stability, etc. Experimental measurement and theoretical prediction on charging timescale for supercapacitors often have large difference. This work develops a matched asymptotic expansion method to derive the charging dynamics of supercapacitors with porous electrodes, in which the supercapacitors are described by the stack-electrode model. Coupling leading-order solutions between every two stacks by continuity of ionic concentration and fluxes leads to an ODE system, which is a generalized equivalent circuit model for zeta potentials, with the potential-dependent nonlinear capacitance and resistance determined by physical parameters of electrolytes, e.g., specific counterion valences for asymmetric electrolytes. Linearized stability analysis on the ODE system after projection is developed to theoretically characterize the charging timescale. The derived asymptotic solutions are numerically verified. Further numerical investigations on the biexponential charging timescales demonstrate that the proposed generalized equivalent circuit model, as well as companion linearized stability analysis, can faithfully capture the charging dynamics of symmetric/asymmetric electrolytes in supercapacitors with porous electrodes.
Comment: 26 pages, 6 figures