In Situ Polymerization Derived from PAN-Based Porous Membrane Realizing Double-Stabilized Interface and High Ionic Conductivity for Lithium-Metal Batteries

Polymer polyacrylonitrile (PAN), with exceptional mechanical strength and ionic conductivity, is considered a potential electrolyte. However, the huge interfacial impedance of PAN-derived C≡N polar nitrile groups and Li anode limited its application. In this study, a double-stabilized interface was integrated by in situ polymerization of DOL between electrodes and a three-dimensional (3D) porous PAN polymer matrix containing SN plasticizer and LLZTO ceramic fillers to optimize the challenge of interfacial instability. The fabricated PDOL-PAN(SN/LLZTO)-PDOL composite solid electrolyte (CSE) exhibited the maximum ionic conductivities of 1.9 × 10–3 S cm–1 at room temperature and 2.5 × 10–3 S cm–1 at 60 °C, an electrochemical stability window (ESW) of 4.9 V, and a high Li+ transference number (tLi+) of 0.65. In addition, the side reactions of the PAN/Li metal were effectively prevented by inserting PDOL between the 3D porous membrane and Li electrode. Benefiting from the superior interface compatibility and ion conductivity, the Li symmetric battery showed more than 2000 h of cyclability. The solid Li/LiFePO4 full battery delivered excellent cycling performance, showing an original specific capacity of 136.2 mAh g–1 with a capacity retention of 90.1% after 350 cycles at 1C and 60 °C. Furthermore, the cycling of solid-state Li/NCM622 batteries also proved their application potential. This work presents an effective approach to solving interface problems of the PAN electrolyte for solid lithium-metal batteries (LMBs).