Enhancement mechanism of the comprehensive performance of all-solid-state polymer electrolytes by halloysite nanotubes: Construction of efficient lithium-ion conduction channels

Considering the current issues with poly(ethylene oxide)-based all-solid-state polymer electrolytes (PEO-ASSPEs) employed in lithium-ion batteries (LIBs), such as low ionic conductivity, low lithium-ion transference number, narrow electrochemical stability window, and poor cyclic stability. This study introduces oxygen-vacancy-rich halloysite nanotubes (HNTs) and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) into the PEO matrix to fabricate a flexible composite polymer electrolyte (CPEs) via a solvent-free method. The interaction between HNTs and LiTFSI in the PEO matrix serves to mitigate the ionic solvation effect, increase the number of free lithium-ion, and reduce the lithium-ion migration energy barrier. Additionally, the internal framework formed by the mutual stacking of HNTs reduces the number of entanglements in polymer molecular chains, enhances the mobility of the chains, and generates a continuous interface effect, forming fast lithium-ion transport channels. The CPEs prepared in this study are in conformity with the Vogel-Tammann-Fulcher (VTF) empirical equation. The CPE containing 10 wt% HNTs exhibits a high ionic conductivity (7.15 × 10−4 S cm−1) at 25 °C, a high lithium-ion transference number (0.600), a wide electrochemical stability window (5.5 V), and excellent cyclic performance (capacity retention of 82.02 % after 100 cycles at 0.1C), satisfying the electrochemical performance requirements for ASSPEs in LIBs.