Bi‐MOF Modulating MnO2 Deposition Enables Ultra‐Stable Cathode‐Free Aqueous Zinc‐Ion Batteries

The Mn-based materials are considered as the most promising cathodes for zinc-ion batteries (ZIBs) due to their inherent advantages of safety, sustainability and high energy density, however suffer from poor cyclability caused by gradual Mn²⁺ dissolution and irreversible structural transformation. The mainstream solution is pre-adding Mn²⁺ into the electrolyte, nevertheless faces the challenge of irreversible Mn²⁺ consumption results from the MnO₂ electrodeposition reaction (Mn²⁺ → MnO₂ ). This work proposes a "MOFs as the electrodeposition surface" strategy, rather than blocking it. The bismuth (III) pyridine-3,5-dicarboxylate (Bi-PYDC) is selected as the typical electrodeposition surface to regulate the deposition reaction from Mn²⁺ to MnO₂ . Because of the unique less hydrophilic and manganophilic nature of Bi-PYDC for Mn²⁺ , a moderate MnO₂ deposition rate is achieved, preventing the electrolyte from rapidly exhausting Mn²⁺ . Simultaneously, the intrinsic stability of deposited R-MnO₂ is enhanced by the slowly released Bi³⁺ from Bi-PYDC reservoir. Furthermore, Bi-PYDC shows the ability to accommodate H⁺ insertion/extraction. Benefiting from these merits, the cathode-free ZIB using Bi-PYDC as the electrodeposition surface for MnO₂ shows an outstanding cycle lifespan of more than 10 000 cycles at 1 mA cm^-2 . This electrode design may stimulate a new pathway for developing cathode free long-life rechargeable ZIBs.