Water-Assisted Ion Conduction in Solid-State Charge-Transfer Complex Electrolytes for Lithium Batteries

Current research on solid-state organic electrolytes mainly focuses on polymer electrolytes where ion transport is facilitated by chain segmental motion. A limited number of prior reports suggest that solid-state electrolytes based on organic charge-transfer (CT) complexes can have surprisingly high ionic conductivity. Here, we report that processing and environmental conditions drastically impact charge transport properties of CT complex electrolytes based on tetrathiafulvalene-tetracyanoquinodimethane (TTF-TCNQ) mixed with lithium bis(trifluoromethylsulfonylimide) (LiTFSI). Thermal annealing and water vapor treatment decreases electronic conductivity and increases ionic conductivity. The electrolyte with 1-1-2-0.45 molar ratio of TTF-TCNQ-LiTFSI-H2O has an ionic conductivity of 2 × 10-3 S/cm at 25 °C with order 104 times lower electronic conductivity. In this system where ion conduction is decoupled from the mobility of the organic phase, thermal annealing helps reduce CT connectivity and expose more surfaces to interact with LiTFSI, and water promotes the dissociation of LiTFSI.