Quasi-Solid-State Ion-Conducting Arrays Composite Electrolytes with Fast Ion Transport Vertical-Aligned Interfaces for All-Weather Practical Lithium-Metal Batteries

The rapid improvement in the gel polymer electrolytes (GPEs) with high ionic conductivity brought it closer to practical applications in solid-state Li-metal batteries. The combination of solvent and polymer enables quasi-liquid fast ion transport in the GPEs. However, different ion transport capacity between solvent and polymer will cause local nonuniform Li⁺ distribution, leading to severe dendrite growth. In addition, the poor thermal stability of the solvent also limits the operating-temperature window of the electrolytes. Optimizing the ion transport environment and enhancing the thermal stability are two major challenges that hinder the application of GPEs. Here, a strategy by introducing ion-conducting arrays (ICA) is created by vertical-aligned montmorillonite into GPE. Rapid ion transport on the ICA was demonstrated by ⁶Li solid-state nuclear magnetic resonance and synchrotron X-ray diffraction, combined with computer simulations to visualize the transport process. Compared with conventional randomly dispersed fillers, ICA provides continuous interfaces to regulate the ion transport environment and enhances the tolerance of GPEs to extreme temperatures. Therefore, GPE/ICA exhibits high room-temperature ionic conductivity (1.08 mS cm⁻¹) and long-term stable Li deposition/stripping cycles (> 1000 h). As a final proof, Li||GPE/ICA||LiFePO₄ cells exhibit excellent cycle performance at wide temperature range (from 0 to 60 °C), which shows a promising path toward all-weather practical solid-state batteries.