Advances in lithium-ion battery electrolyte materials have created a niche for the evolution of various electrochemical techniques. Appropriate diagnostic techniques to evaluate new electrolytes are of paramount importance, as the conventional techniques lead to prejudiced conclusions. Organic–inorganic hybrid ion gels, employed as electrolytes for the carbon anodic half-cell, showing discrepancies in its charge discharge profile, were probed for their abnormal charge–discharge behaviour. Dynamic electrochemical impedance spectroscopy (DEIS) was used as a diagnostic tool; inferences were drawn from charge-transfer resistance values and used as indicators to delimit the potential boundaries for optimum performance of the cells. Identifying the cut-off potentials through DEIS and subsequent charge–discharge provided clean profiles.