%0 Journal Article %A Hoffknecht, Jan-Philipp %A Wettstein, Alina %A Atik, Jaschar %A Krause, Christian %A Thienenkamp, Johannes %A Brunklaus, Gunther %A Winter, Martin %A Diddens, Diddo %A Heuer, Andreas %A Paillard, Elie %T Coordinating Anions “to the Rescue” of the Lithium Ion Mobility in Ternary Solid Polymer Electrolytes Plasticized With Ionic Liquids %J Advanced energy materials %V 13 %N 1 %@ 1614-6832 %C Weinheim %I Wiley-VCH %M FZJ-2023-01300 %P 2202789 - %D 2023 %X 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. %F PUB:(DE-HGF)16 %9 Journal Article %U <Go to ISI:>//WOS:000888918600001 %R 10.1002/aenm.202202789 %U https://juser.fz-juelich.de/record/1005101