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Temperature-Dependence of the Solid-Electrolyte Interphase Overpotential: Part I. Two Parallel Mechanisms, One Phase Transition

Authors: Michael Hess;

Temperature-Dependence of the Solid-Electrolyte Interphase Overpotential: Part I. Two Parallel Mechanisms, One Phase Transition

Abstract

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

Country
Switzerland
Related Organizations
Keywords

Chemical Physics (physics.chem-ph), Condensed Matter - Materials Science, Materials Science (cond-mat.mtrl-sci), FOS: Physical sciences, Physics - Applied Physics, Applied Physics (physics.app-ph), Physics - Chemical Physics

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citations
This is an alternative to the "Influence" indicator, which also reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Citations provided by BIP!
popularity
This indicator reflects the "current" impact/attention (the "hype") of an article in the research community at large, based on the underlying citation network.
BIP!Popularity provided by BIP!
influence
This indicator reflects the overall/total impact of an article in the research community at large, based on the underlying citation network (diachronically).
BIP!Influence provided by BIP!
impulse
This indicator reflects the initial momentum of an article directly after its publication, based on the underlying citation network.
BIP!Impulse provided by BIP!
17
Top 10%
Average
Top 10%
Green
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