Functionally Modified Polymer Electrolyte Based on Noncovalent Interaction for Stable Lithium Metal Batteries

The charge transfer efficiency of the solid electrolyte depends on the number of lithium ions that can be effectively transported and participate in the electrode reaction. However, limited by the strong coupling relationship between Li⁺ and Lewis basic sites on the polymer chain, the Li⁺ transference number (t_Li) of the solid polymer electrolyte (SPE) based dual-ion conductor is typically low, resulting in excessive anion aggregation at the electrode side and inducing concentration polarization. In this study, we present a functionalized modified polymer electrolyte (FMPE) with selective cation transport, which was synthesized by embedding 4-(trifluoromethyl)styrene (TFS) functionalized groups onto the poly(diethylene glycol diacrylate) polymer chain. The TFS group formed noncovalent couplings with TFSI^- anions through hydrogen bondings and dipole-dipole interactions, which effectively limited the migration of the anions and contributed to the elevated t_Li of the FMPEs to 0.595 and 0.699 at 25 and 60 °C, respectively. Density functional theory (DFT) calculations were performed to verify the increased anion migration barriers for different noncovalent interactions and revealed that the conjugated system formed by the delocalized π electrons of the benzene ring and the C═O groups helped to disperse the electron distribution of the polymer chains. Consequently, the decrease in the degree of Li⁺ immobilization promotes the decoupling and migration of Li⁺ between the polymer chains. Benefiting from optimized Li⁺ transport behavior, the lithium metal batteries (LMBs) assembled by FMPEs and LiFePO₄ exhibit excellent rate performance (discharge specific capacity of 88.8 mAh g^-1 at 5 C) and stable long-term cycle performance (capacity decay rate of only 0.064% per cycle for 500 cycles at 25 °C and 0.5 C).