Solvent‐Free Metal–Organic Framework‐Based Porous Liquid Electrolyte for Ultrahigh‐Temperature (180°C) Zn Metal Batteries

ABSTRACT Zn metal batteries capable of withstanding ultrahigh temperatures are urgently needed across diverse fields, yet their development is hindered by the poor thermal adaptability of conventional electrolytes. Herein, we develop an innovative electrolyte paradigm represented by a metal–organic framework (MOF)‐based porous liquid electrolyte (PLE) without active organic or H 2 O solvents, which enables long‐term operation of Zn metal batteries at 180°C for the first time. Modeled on UiO‐66, PLE combines permanent microporosity with liquid fluidity, offering non‐flammability, thermal stability, and anode compatibility. The permanent micropores of the UiO‐66 skeleton provide ordered nanoconfined ion transport channels, while flexible grafted polymeric chains offer coordination‐dissociation hopping sites, and ultimately suppress dendrite growth even at high temperatures. Zn||Zn symmetric cells deliver ultra‐long cycling lifespans of 10 000 h at 25°C, 4000 h at 120°C, 2100 h at 150°C, and 600 h at 180°C, far surpassing state‐of‐the‐art Zn battery electrolytes. Zn||V 2 O 5 batteries deliver stable performance across 25−180°C. Moreover, the pore structure of PLE effectively adsorbs polyiodides and polysulfides, enabling high‐temperature Zn||I 2 batteries and, remarkably, extending to Li||S (80°C) and Li||V 2 O 5 batteries (180°C). This work enriches the design philosophy of functional electrolytes and breaks the long‐standing temperature barrier of metal batteries.