A Low‐Cost Quasi‐Solid‐State “Water‐in‐Swelling‐Clay” Electrolyte Enabling Ultrastable Aqueous Zinc‐Ion Batteries

The poor reversibility of Zn metal anodes arising from water‐induced parasitic reactions poses a significant challenge to the practical applications of aqueous zinc‐ion batteries (AZIBs). Herein, a novel quasi‐solid‐state “water‐in‐swelling‐clay” electrolyte (WiSCE) containing zinc sulfate and swelling clay, bentonite (BT), is designed to enable highly reversible Zn metal anodes. AZIB full cells based on the WiSCE exhibit excellent cyclic stability at various current densities, long shelf life, low self‐discharge rate, and outstanding high‐temperature adaptability. Particularly, the capacity of WiSCE‐based AZIB full cells retains 90.47% after 200 cycles at 0.1 A g−1, 96.64% after 2000 cycles at 1 A g−1, and 88.29% after 5000 cycles at 3 A g−1. Detailed density functional theory calculations show that strong hydrogen bonds are formed between BT and water molecules in the WiSCE. Thus, water molecules are strongly confined by BT, particularly within the interlayers, which significantly inhibits water‐induced parasitic reactions and greatly improves cyclic stability. Compared to the state‐of‐the‐art “water‐in‐salt” electrolytes, the WiSCE can provide a significantly higher capacity at the full‐cell level with a substantially reduced cost, which is promising for the design of next‐generation high‐performance AZIBs. This work provides a new direction for developing cost‐competitive AZIBs as alternatives to grid‐scale energy storage. A low‐cost quasi‐solid‐state “water‐in‐swelling‐clay” electrolyte (WiSCE) based on bentonite is designed to improve the electrochemical performance of aqueous zinc‐ion batteries (AZIBs). The activities of water molecules are effectively suppressed by confining them within the interlayer spaces of bentonite crystals, ensuring the stable cycling, low self‐discharge rate, and long shelf life of the WiSCE‐based AZIBs.