Coordinating Anions “to the Rescue” of the Lithium Ion Mobility in Ternary Solid Polymer Electrolytes Plasticized With Ionic Liquids

Abstract Lithium salts with low coordinating anions such as bis(trifluoromethanesulfonyl)imide (TFSI) have been the state‐of‐the‐art for polyethylene oxide (PEO)‐based “dry” polymer electrolytes for 3 decades. Plasticizing PEO with TFSI‐based ionic liquids (ILs) to form ternary solid polymer electrolytes (TSPEs) increases conductivity and Li⁺ diffusivity. However, the Li⁺ transport mechanism is unaffected compared to their “dry” counterparts and is essentially coupled to the dynamics of the polymer host matrix, which limits Li⁺ transport improvement. Thus, a paradigm shift is hereby suggested: the utilization of more coordinating anions such as trifluoromethanesulfonyl‐N‐cyanoamide (TFSAM), able to compete with PEO for Li⁺ solvation, to accelerate the Li⁺ transport and reach a higher Li⁺ transference number. The Li–TFSAM interaction in binary and ternary TFSAM‐based electrolytes is probed by experimental methods and discussed in the context of recent computational results. In PEO‐based TSPEs, TFSAM drastically accelerates the Li⁺ transport (increases Li⁺ transference number by a factor 6 and the Li⁺ conductivity by 2–3) and computer simulations reveal that lithium dynamics are effectively re‐coupled from polymer to anion dynamics. Last, this concept of coordinating anions in TSPEs is successfully applied in LFP||Li metal cells leading to enhanced capacity retention (86% after 300 cycles) and an improved rate performance at 2C.