Highly Conductive and Stable Composite Polymer Electrolyte with Boron Nitride Nanotubes for All‐Solid‐State Lithium Metal Batteries

Abstract

All-solid-state lithium metal batteries (ASSLMBs) have emerged as the most promising next-generation energy storage devices. However, the unsatisfactory ionic conductivity of solid electrolytes at room temperature has impeded the advancement of solid-state batteries. In this work, a multifunctional composite solid electrolyte (CSE) is developed by incorporating boron nitride nanotubes (BNNTs) into polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP). BNNTs, with a high aspect ratio, trigger the dissociation of Li salts, thus generating a greater population of mobile Li⁺, and establishing long-distance Li⁺ transport pathways. PVDF-HFP/BNNT exhibits a high ionic conductivity of 8.0 × 10^-4 S cm^-1 at room temperature and a Li⁺ transference number of 0.60. Moreover, a Li//Li symmetric cell based on PVDF-HFP/BNNT demonstrates robust cyclic performance for 3400 h at a current density of 0.2 mA cm^-2. The ASSLMB formed from the assembly of PVDF-HFP/BNNT with LiFePO₄ and Li exhibits a capacity retention of 93.2% after 850 cycles at 0.5C and 25 °C. The high-voltage all-solid-state LiCoO₂/Li cell based on PVDF-HFP/BNNT also exhibits excellent cyclic performance, maintaining a capacity retention of 96.4% after 400 cycles at 1C and 25 °C. Furthermore, the introduction of BNNTs is shown to enhance the thermal conductivity and flame retardancy of the CSE.