Vertically aligned 2D materials filler for solid polymer electrolytes is demonstrated. The aligned, continuous, run‐through polymer‐filler interfaces enhance the ionic conductivity, Li+ transference number, mechanical modulus, and electrochemical stability of solid polymer electrolytes. LiFePO4 in lithium metal batteries with the electrolyte could deliver a specific capacity of 167 mAh g−1 at 0.1 C at 35 °C. Abstract Solid state lithium metal batteries are the most promising next‐generation power sources owing to their high energy density and safety. Solid polymer electrolytes (SPE) have gained wide attention due to the excellent flexibility, manufacturability, lightweight, and low‐cost processing. However, fatal drawbacks of the SPE such as the insufficient ionic conductivity and Li+ transference number at room temperature restrict their practical application. Here vertically aligned 2D sheets are demonstrated as an advanced filler for SPE with enhanced ionic conductivity, Li+ transference number, mechanical modulus, and electrochemical stability, using vermiculite nanosheets as an example. The vertically aligned vermiculite sheets (VAVS), prepared by the temperature gradient freezing, provide aligned, continuous, run‐through polymer‐filler interfaces after infiltrating with polyethylene oxide (PEO)‐based SPE. As a result, ionic conductivity as high as 1.89 × 10−4 S cm−1 at 25 °C is achieved with Li+ transference number close to 0.5. Along with their enhanced mechanical strength, Li|Li symmetric cells using VAVS–CSPE are stable over 1300 h with a low overpotential. LiFePO4 in all‐solid‐state lithium metal batteries with VAVS–CSPE could deliver a specific capacity of 167 mAh g−1 at 0.1 C at 35 °C and 82% capacity retention after 200 cycles at
Published in: "Advanced Functional Materials".