Alternate Storage of Opposite Charges in Multisites for High‐Energy‐Density Al–MOF Batteries

Abstract The limited active sites of cathode materials in aluminum‐ion batteries restrict the storage of more large‐sized Al‐complex ions, leading to a low celling of theoretical capacity. To make the utmost of active sites, an alternate storage mechanism of opposite charges (AlCl₄⁻ anions and AlCl₂⁺ cations) in multisites is proposed herein to achieve an ultrahigh capacity in Al–metal–organic framework (MOF) battery. The bipolar ligands (oxidized from 18π to 16π electrons and reduced from 18π to 20π electrons in a planar cyclic conjugated system) can alternately uptake and release AlCl₄⁻ anions and AlCl₂⁺ cations in charge/discharge processes, which can double the capacity of unipolar ligands. Moreover, the high‐density active Cu sites (Cu nodes) in the 2D Cu‐based MOF can also store AlCl₂⁺ cations for a higher capacity. The rigid and extended MOF structure can address the problems of high solubility and poor stability of small organic molecules. As a result, three‐step redox reactions with two‐electron transfer in each step are demonstrated in charge/discharge processes, achieving high reversible capacity (184 mAh g⁻¹) and energy density (177 Wh kg⁻¹) of the optimized cathode in an Al–MOF battery. The findings provide a new insight for the rational design of stable high‐energy Al–MOF batteries.