A Protophilic MOF Enables Ni‐Rich Lithium‐Battery Stable Cycling in a High Water/Acid Content

Abstract Trace protic impurities, such as water and hydrofluoric acid (HF), can severely degrade the stable and long cycling of lithium batteries. Therefore, the costly water removal process is inevitably needed throughout production of lithium batteries, leaving the paradox that energy‐saving lithium‐battery technology consumes non‐negligible amounts of energy. Herein, a unique ionic metal–organic framework (MOF) is reported that enables highly destructive H₂O/HF‐tolerant lithium batteries. The isolated ionic fluorine sites in the MOF exhibit unusual protophilicity and efficiently capture ppm‐levels H₂O/HF from the highly polar electrolyte solvents. The resulting MOF‐based LiNi_0.6Mn_0.2Co_0.2O₂│Li battery achieves over 300 cycles in the presence of 800 ppm H₂O or 1107 ppm acidic impurity. This tenfold longer battery lifespan relative to those for batteries with conventional standard separators demonstrates its excellent electrochemical cycling performance. The results reveal that the rational use of unique nanoporous features of MOFs can provide new possibilities for long‐standing challenges in the lithium‐battery industry.