Bo Long, Feng Wu, Yu Li, Yu Li, Hao Wang, Wei Liu, Ying Li, Ying Li, Qiaojun Li, Qiannan Zhou, Ying Bai, Chuan Wu
Understanding the dynamic evolution of the aluminum anode interface in ionic liquid electrolytes is crucial for the large-scale application of rechargeable aluminum batteries (RABs). Herein, we use a series of advanced in situ characterizations to reveal a dendrite-to-corrosion transition, demonstrating that imidazolium cations (EMI + ) fundamentally dominate anode degradation and instability. Therefore, based on a differential access mechanism, we engineer a metal–organic framework (MOF-C) layer with molecular-scale nanochannels that selectively block corrosive EMI + while accelerating AlCl 4 – diffusion. The modified Al/MOF-C anode achieves an unprecedented cycling stability of >11,000 h (at 1 mA cm –2 with minimal 20 mV overpotential) in symmetric cells, far exceeding all previous reports (typically <2000 h). Matched with natural graphite cathodes, full cells retain 95% capacity over 500 cycles. This work not only resolves the long-standing interfacial dispute in RABs but also establishes an ingenious solution aligned with interfacial evolution for next-generation stable metal anodes.