High Lithium Salt Content PVDF‐Based Solid‐State Composite Polymer Electrolyte Enhanced by h‐BN Nanosheets

Abstract Due to the unique safety qualities, solid composite polymer electrolyte (SCPE) has achieved considerable attentions to fabricate high‐energy‐density lithium metal batteries, but its overall performance still has to be improved. Herein, a high lithium salt content poly(vinylidene fluoride) (PVDF)‐based SCPE was developed, enhanced by hexagonal boron nitride (h‐BN) nanosheets, presenting perfect electrochemical performance, fast ion transport, and efficient inhibition of lithium dendrite growth. The optimized SCPE (PVDF‐L70‐B5) could deliver high ionic conductivity (2.98×10 −4 S cm −1 ), ultra‐high Li + ion transfer number (0.62), wide electrochemical stability window (5.24 V), and strong mechanical strength (3.45 MPa) at room temperature. Density functional theory calculation further confirmed that the presence of h‐BN could promote the dissociation of bis(trifluoromethanesulfonyl)imide lithium (LiTFSI) and the rapid transfer of Li + ions. As a result, the assembled symmetric Li/Li battery and asymmetric Li/LiFePO 4 battery using PVDF‐L70‐B5 SCPEs both exhibited high reversible capacity, long‐term cycle stability, and high‐rate performance when cycled at 60 or 30 °C. The designed SCPEs will open up a new route to synthesize solid‐state lithium batteries with high energy density and high safety.