Highly conductive and mechanically robust single-ion conducting polymer electrolyte membranes with a high concentration of charge carriers for dendrite-proof lithium metal batteries

Abstract

Single-ion polymer electrolytes (SIPEs) with high Li-ion transference number (tLi+≈1) are promising candidates for inhibiting the growth of lithium dendrites in lithium metal batteries (LMBs). However, it remains challenging to develop SIPEs applicable to high-performance LMBs due to their relatively low ionic conductivity and poor mechanical strength. Herein, an aromatic single-ion conductor (LiPSBI) with high Li-ion concentration is elaborately designed, yielding porous and mechanically robust SIPE membranes (NSIPM) when mixed with aliphatic poly (vinylidene fluoride-hexafluoropropylene) P(VDF-HFP) binder via “structural self-assembly” method. As expected, the as-prepared NSIPM porous membranes can simultaneously exhibit a high porosity of 41.4%, a considerable organic solvent uptake of 181.0%, and excellent mechanical strength of 20.5 MPa. Notably, the LiPSBI-based gel NSIPM demonstrates an ionic conductivity of 8.15 × 10−5 S cm−1 at 25 °C, which is almost twice that of the single-ion electrolyte with low Li-ion concentration (4.74 × 10−5 S cm−1). Consequently, the Li||LiFePO4 cells using the gel NSIPM display remarkable cycling durability for several hundred cycles while delivering high discharge specific capacities of 148.4 mA h g−1 and 122.9 mA h g−1 at 0.2C and 1 C, respectively. In addition, the Li/Li symmetric cells assembling the gel NSIPM can effectively alleviate concentration polarization and inhibit the lithium dendrites growth, which is responsible for an exceptionally steady striping/plating process with a low overpotential over 1300 h at 2.5 mA cm−1 at 25 °C. This work provides a new strategy to prepare high-performance SIPEs by increasing the concentration of charge carriers.