Going Beyond Sweep Voltammetry: Alternative Approaches in Search of the Elusive Electrochemical Stability of Polymer Electrolytes

Solid polymer electrolytes (SPEs) are promising candidates for solid-state lithium-ion batteries. Potentially, they can be used with lithium metal anodes and high-voltage cathodes, provided that their electrochemical stability is sufficient. Thus far, the oxidative stability has largely been asserted based on results obtained with sweep voltammetry, which are often determined and reliant on arbitrary assessments that are highly dependent on the experimental conditions and do not take the interaction between the electrolyte and the electrode material into account. In this study, alternative techniques are introduced to address the pitfalls of sweep voltammetry for determining the oxidative stability of SPEs. Staircase voltammetry involves static conditions and eliminates the kinetic aspects of sweep voltammetry, and coupled with impedance spectroscopy provides information of changes in resistance and interphase layer formation. Synthetic charge–discharge profile voltammetry applies the real voltage profile of the active material of interest. The added effect of the electrode active material is investigated with a cut-off increase cell cycling method where the upper cut-off voltage during galvanostatic cycling is gradually increased. The feasibility of these techniques has been tested with both poly(ethylene oxide) and poly(trimethylene carbonate) combined with LiTFSI, thereby showing the applicability for several categories of SPEs.