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_0.8Co_0.1Mn_0.1O₂ 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.