Enhanced Li+ and Mg2+ Diffusion at the Polymer–Ionic Liquid Interface within PVDF‐Based Ionogel Electrolytes for Batteries and Metal‐Ion Capacitors

With the widespread use of batteries, their increased performance is of growing in importance. One avenue for this is the enhancement of ion diffusion, particularly for solid‐state electrolytes, for different ions such as lithium (Li+) and magnesium (Mg2+). Unraveling the origin of better cation diffusion in confined ionic liquids (ILs) in a polymer matrix (ionogels) is compared to that of the IL itself. Ionic conductivity measured by electrochemical impedance spectroscopy for ionogels (7.0 mS cm−1 at 30 °C) is very close to the conductivity of the non‐confined IL (8.9 mS cm−1 at 30 °C), that is, 1‐ethyl‐3‐methyimidazolium bis(trifluorosulfonyl)imide (EMIM TFSI). An even better ionic conductivity is observed for confined EMIM TFSI with high concentrations (1 m) of lithium or magnesium salt added. The improved macroscopic transport properties can be explained by the higher self‐diffusion of each ion at the liquid‐to‐solid interface induced by the confinement in a poly‐vinylidenedifluoride (PVDF) polymer matrix. Upon confinement, the strong breaking down of ion aggregates enables a better diffusion, especially for TFSI anion and strongly polarizing cations (e.g., Li+, Mg2+.). The coordination number of these cations in the liquid phase confirmed that Li+ and Mg2+ interact with the polymer matrix. Moreover, it is a major result that the activation energy for diffusion is lowered. Greater ion diffusion in the EMIMTFSI ionic liquid is demonstrated thanks to the confinement of the liquid in a PVDF polymer matrix, leading to improved transport properties. The polymer‐ionic liquid interface is favorable to the disaggregation of metal cation and anion clusters, with facilitated diffusion into Li and Mg solid‐state electrolytes.