• Energy Research

It has been shown recently that the overpotential originating from ionic conduction of alkali-ions through the inner dense solid-electrolyte interphase (SEI) is strongly non-linear. An empirical equation was proposed to merge the measured resistances from both galvanostatic cycling (GS) and electrochemical impedance spectroscopy (EIS) at 25$^{\circ}$C. Here, this analysis is extended to the full temperature range of batteries from -40$^{\circ}$C to +80$^{\circ}$C for Li, Na, K and Rb-metal electrodes in carbonate electrolytes. Two different transport mechanisms are found. The first one conducts alkali-ions at all measured temperatures. The second transport mechanism conducts ions for all seven measured Li-ion electrolytes and one out of four Na-ion electrolytes, however, only above a certain critical temperature $T_C$. At $T_C$ a phase transition is observed switching-off the more efficient transport mechanism and leaving only the general ion conduction mechanism. The associated overpotentials increase rapidly below $T_C$ depending on alkali-ion, salt and solvent and become a limiting factor during galvanostatic operation of all Li-ion electrolytes at low temperature. In general, the current analysis merges the SEI resistances measured by EIS ranging from 26 $��$cm$^2$ for the best Li up to 292 M$��$cm$^2$ for Rb electrodes to its galvanostatic response over seven orders of magnitude. The determined critical temperatures are between 0-25$^{\circ}$C for the tested Li and above 50$^{\circ}$C for Na electrolytes. 10 pages, 7 figures, file includes Suppl Info, http://jes.ecsdl.org/content/165/2/A323