Dynamic Effect of Overscreening on Electrochemical and Thermal Properties of EDLC Electrodes during Charging/Discharging Cycles

Overscreening was commonly observed during charging/discharging cycles of electric double layer capacitors(EDLCs). This study presented a two-dimensional continuum electrochemical thermal model with a distribution function for concentration considering overscreening to investigate how overscreening affected the dynamic formation of electric double layer (EDL) near electrodes in macroscale. The results indicated that ion distribution was co-affected by EDL formation and overscreening near the electrode. Correspondingly, layered space charge density distribution resulted in a thicker diffuse layer, whose thickness was determined by the sum of co-ion and counter-ion diameters. Additionally, the diffuse layer capacitance was proportional to the reciprocal of counter-ion diameter, while the total capacitance was proportional to a linear combination of counter-ion and the larger ion diameters. Moreover, the shift from endothermic to exothermic for the total heat generation rate was dominated by heat of mixing, and was caused by the local ion mixing due to overscreening, resulting in local entropy increase. The results of this study can be used to further investigate the effect of overscreening on ion transient transport dynamic and heat generation rates.