Fine-Tuning Electrolyte Concentration and Metal-Organic Framework Surface Toward Actuating Fast Zn2+ Dehydration for Aqueous Zn-Ion Batteries

Functional porous coating on zinc electrode is emerging as a powerful ionic sieve to suppress dendrite growth and side reactions, thereby improving highly reversible aqueous zinc ion batteries. However, the ultrafast charge rate is limited by the substantial cation transmission strongly associated with dehydration efficiency. Here, we unveil the entire dynamic process of solvated Zn 2+ ions’ continuous dehydration from electrolyte across the MOF‐electrolyte interface into channels with the aid of molecular simulations, taking zeolitic imidazolate framework ZIF‐7 as proof‐of‐concept. The moderate concentration of 2 M ZnSO 4 electrolyte being advantageous over other concentrations possesses the homogeneous water‐mediated ion pairing distribution, resulting in the lowest dehydration energy, which elucidates the molecular mechanism underlying such concentration adopted by numerous experimental studies. Furthermore, we show that modifying linkers on the ZIF‐7 surface with hydrophilic groups such as −OH or −NH 2 can weaken the solvation shell of Zn 2+ ions to lower the dehydration free energy by approximately 1 eV, and may improve the electrical conductivity of MOF. These results shed light on the ions delivery mechanism and pave way to achieve long‐term stable zinc anodes at high capacities through atomic‐scale modification of functional porous materials.