Interfacial Microgel Self‐Assembly Engineered for Superionic Conduction in PVDF Electrolyte

In this work, we propose an ion‐mediated interfacial microgel self‐assembly strategy, enabling the construction of a conduction network with optimized ion coordination to overcome the intrinsic limitations of PVDF‐based electrolytes. As prepared M (D) —PVDF‐HFP electrolyte shows remarkable ionic conductivity (4.54 × 10 −4 S cm −1 at room temperature), high Li + transference number (0.63), and a 4.8 V‐wide operating window. Galvanostatic electrochemical impedance spectroscopy and finite element method simulations demonstrate rapid response and a high and uniform Li + flux under operating conditions. Consequently, symmetric cells display stable Li plating/stripping for >5,000 h with an overpotential of only 136.4 mV at 0.1 mA cm −2 (25 °C). Furthermore, all‐solid‐state cells employing a LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathode delivered an initial reversible specific capacity of 181.08 mAh g −1 , even under a high areal capacity load of approximately 2.0 mAh cm −2 . Our work is an innovative exploration to induce uniform Li + flux in heterogeneous polymer electrolyte and highlights the importance of internal interface behavior in solid‐state polymer electrolytes.