Designing a Refined Multi‐Structural Polymer Electrolyte Framework for Highly Stable Lithium‐Metal Batteries

Rational structural designs of solid polymer electrolytes featuring rich interface‐phase morphologies can improve electrolyte connection and rapid ion transport. However, these rigid interfacial structures commonly result in diminished or entirely inert ionic conductivity within their bulk phase, compromising overall electrolyte performance. Herein, a multi‐component ion‐conductive electrolyte was successfully designed based on a refined multi‐structural polymer electrolyte (RMSPE) framework with uniform Li+ solvation chemistry and rapid Li+ transporting kinetics. The RMSPE is constructed via polymerization‐induced phase separation based on a rational combination of lithiophilic components and rigid/flexible chain units with significant hydrophobic/hydrophilic contrasts. Further refined by coating a robust polymer network, this all‐organic design endows a homogenous micro‐nano porous structure, providing a novel framework favorable for rapid ion transport in both its soft interfacial and bulk phases. The RMSPE exhibited excellent ion conductivity of 1.91 mS cm−1 at room temperature and a high Li+ transference number of 0.7. Assembled symmetrical Li cells realized stable cycling for over 2400 h at 3.0 mA cm−2. LiFePO4 full batteries demonstrated a long lifespan of 3300 cycles with a capacity retention of 93.5% and stable cycling performance at −35 °C. This innovative design concept offers a promising perspective for achieving high‐performance polymer‐based Li metal batteries.