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

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.