Overlimiting Currents and Sand’s Time Behaviors in Solid Polymer Electrolytes

Abstract

Dendrite growth in solid polymer electrolytes has been frequently analyzed since it was the critical issue that limited its applications. For the liquid electrolyte systems, the dilute solution theory and the classic Nernst-Planck equation have been proven to be useful tools for analysis of ion transport dynamics and especially the dendrite initiation at Sand’s time. However, characterization of the Sand’s time in solid polymer electrolyte systems is challenging and also seldomly performed. From the experimental perspective, operando observations have been done, but the true local current density was different from the geometrical average current density since there was always heterogeneous current distribution for millimeter-scale electrolytes. From the theoretical perspective, the dendrite initiation time followed the trend predicted by Sand’s equation, but discrepancies were found such as dendrites observed at under-limiting currents or the order-of-magnitude extended Sand’s time compared to theoretical predictions. Here, we use transparent microcapillary cells for solid polymer electrolyte systems to overcome these challenges. These specialized cells allow direct operando optical observations, while the micron-scale cross-sectional area minimizes the discrepancy between true local and averaged geometrical current densities. Comparison between operando image and voltage response during constant current polarization shows that, unlike liquid electrolyte cases, the dendrite initiation for solid polymer electrolytes doesn’t always trigger a voltage spike. We also derived transport parameters from the measured Sand’s time, limiting current density, and conductivity and the cross-validated transport parameters were used to calculate theoretical Sand’s time that can be compared with the experimental values. Using the analytical solution from the Nernst-Planck equation and numerical calculations using Newman’s concentrated solution model and COMSOL Multiphysics, the predicted Sand’s time for the dilute and concentrated solution theory both matched closely with our experimental values. This work demonstrates that while the polarization process and the onset of lithium dendritic growths in solid polymer electrolytes can be still accurately predicted by the dilute solution theory, it may not always result in voltage responses similar to that of the liquid electrolyte cases. It’s also suggested that ensuring the homogenous distribution of lithium flux and avoiding the localized overlimiting current density is the key to realizing the dendrite-free polymer electrolytes.