Conformational Regulation of Dielectric Poly(Vinylidene Fluoride)‐Based Solid‐State Electrolytes for Efficient Lithium Salt Dissociation and Lithium‐Ion Transportation

Abstract Restricted by the poor ability of polymers to dissociate lithium salts and transport ions, solid‐state polymer electrolytes (SPEs) show extremely low ionic conductivities (≈10 −7 –10 −5 S cm −1 ) and transference number of lithium ions ( t Li+ ≈0.2–0.4) at 25 °C. Here, a novel polymer matrix of SPEs that simultaneously promotes lithium salt dissociation and ion transportation based on a high dielectric poly(vinylidene fluoride‐trifluoroethylene‐chlorotrifluoroethylene) (TerP) and an all‐ trans conformational poly(vinylidene fluoride‐trifluoroethylene) (CoP), is developed. The high dielectric constant increases the polarity of CH 2 CF 2 polar groups; then, brings a strong electronegative end that dissociates Li + from lithium salts. The all‐ trans conformation assures all fluorine atoms locate on one side of the chain, constructing ion hopping highways. As a result, the TerP/CoP (TC) SPE exhibits a high ionic conductivity (2.37 × 10 −4 S cm −1 ) and a quite large t Li + of 0.61 at 25 °C. The Li/TC SPE/Li symmetric cells cycle stably for more than half a year (>4500 h) and the LiNi 0.8 Co 0.1 Mn 0.1 O 2 /TC SPE/Li cell cycles steadily for 1000 and 600 cycles at 1 C and 2 C at 25 °C, respectively. This work paves a new way to prepare high‐performance SPEs by simultaneously modulating dielectric constants and conformation of polymers.