MOF‐Enabled Ion‐Regulating Gel Electrolyte for Long‐Cycling Lithium Metal Batteries Under High Voltage

High-voltage lithium metal batteries (LMBs) are a promising high-energy-density energy storage system. However, their practical implementations are impeded by short lifespan due to uncontrolled lithium dendrite growth, narrow electrochemical stability window, and safety concerns of liquid electrolytes. Here, a porous composite aerogel is reported as the gel electrolyte (GE) matrix, made of metal-organic framework (MOF)@bacterial cellulose (BC), to enable long-life LMBs under high voltage. The effectiveness of suppressing dendrite growth is achieved by regulating ion deposition and facilitating ion conduction. Specifically, two hierarchical mesoporous Zr-based MOFs with different organic linkers, that is, UiO-66 and NH2 -UiO-66, are embedded into BC aerogel skeletons. The results indicate that NH2 -UiO-66 with anionphilic linkers is more effective in increasing the Li+ transference number; the intermolecular interactions between BC and NH2 -UiO-66 markedly increase the electrochemical stability. The resulting GE shows high ionic conductivity (≈1 mS cm-1 ), high Li+ transference number (0.82), wide electrochemical stability window (4.9 V), and excellent thermal stability. Incorporating this GE in a symmetrical Li cell successfully prolongs the cycle life to 1200 h. Paired with the Ni-rich LiNiCoAlO2 (Ni: Co: Al = 8.15:1.5:0.35, NCA) cathode, the NH2 -UiO-66@BC GE significantly improves the capacity, rate performance, and cycle stability, manifesting its feasibility to operate under high voltage.