Vertically Aligned Ion Pathways for Fast Conduction and Uniform Lithium Deposition in Solid‐State Batteries

The random distribution of one‐dimensional nanofillers in composite polymer electrolytes (CPEs) typically results in tortuous ion transport pathways, severely limiting ionic conductivity and Li⁺ flux uniformity. Herein, an innovative electric field‐assisted strategy is proposed to construct vertically aligned ion channels in CPEs using lithiated halloysite nanotubes (HNTs–SO₃Li) embedded within a polyurethane acrylate/polyethylene glycol diacrylate (PUA/PEGDA) matrix. Under an alternating electric field, the nanotubes orient perpendicularly, forming continuous, low‐tortuosity pathways that significantly enhance room‐temperature ionic conductivity. The aligned structure not only shortens Li⁺ transport distances but also homogenizes ion flux at the electrode interface, effectively suppressing lithium dendrite growth. Electrochemical characterization reveals exceptional stability. Three‐dimensional structural reconstruction and ion transport simulations further demonstrate that the ordered channels promote uniform Li⁺ distribution and faster ion kinetics compared to disordered systems. This study provides a scalable and efficient approach to designing high‐performance CPEs for next‐generation solid‐state batteries, addressing critical challenges in ionic conductivity, interfacial stability, and dendrite suppression.