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

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.

Enhanced Ion Conduction via Epitaxially Polymerized Two-Dimensional Conducting Polymer for High-Performance Cathode in Zinc-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) are one of the promising choices for the future large-scale grid energy storage, in which Mn-based cathode materials have the advantages of low cost and environmental friendliness. However, their capacity delivery and cycling stability are limited by the large bulk-induced incomplete zincation and structure pulverization. Here, we develop a strategy of epitaxial polymerization in the liquid phase to fabricate two-dimensional (2D) MnOx/polypyrrole nanosheets to enhance the zinc-ion storage by realizing the efficient utilization of active materials and improving the structural stability via a polymerized framework. An ultrahigh capacity of 408 mAh g-1 is demonstrated at 1C rate, and an excellent capacity retention of 78% is realized after 2800 cycles at 5C rate for the AZIB. Electrochemical and morphological characterizations reveal that the unique 2D structure contributes to both the electron/ion conductivity and structural stability. The epitaxial polymerization of the conducting polymer in the liquid phase provides a new perspective to the synthesis of high-performance electrode materials and 2D conducting polymers.