Gradient Quasi‐Solid Electrolyte Enables Selective and Fast Ion Transport for Robust Aqueous Zinc‐Ion Batteries

Abstract The quasi‐solid electrolytes (QSEs) attract extensive attention due to their improved ion transport properties and high stability, which is synergistically based on tunable functional groups and confined solvent molecules among the polymetric networks. However, the trade‐off effect between the polymer content and ionic conductivity exists in QSEs, limiting their rate performance. In this work, the epitaxial polymerization strategy is used to build the gradient hydrogel networks (GHNs) covalently fixed on zinc anode. Then, it is revealed that the asymmetric distribution of negative charges benefits GHNs with fast and selective ionic transport properties, realizing a higher Zn²⁺ transference number of 0.65 than that (0.52) for homogeneous hydrogel networks (HHNs) with the same polymer content. Meanwhile, the high‐density networks formed at Zn/GHNs interface can efficiently immobilize free water molecules and homogenize the Zn²⁺ flux, greatly inhibiting the water‐involved parasitic reactions and dendrite growth. Thus, the GHNs enable dendrite‐free stripping/plating over 1000 h at 8 mA cm⁻² and 1 mAh cm⁻² in a Zn||Zn symmetric cell, as well as the evidently prolonged cycles in various full cells. This work will shed light on asymmetric engineering of ion transport channels in advanced quasi‐solid battery systems to achieve high energy and safety.