High‐Performance Rechargeable Aluminum‐Ion Batteries Enabled by Composite FeF3 @ Expanded Graphite Cathode and Carbon Nanotube‐Modified Separator

Rechargeable aluminum ion batteries (AIBs) are one of the most promising battery technologies for future large‐scale energy storage due to their high theoretical volumetric capacity, low‐cost, and high safety. However, the low capacity of the intercalation‐type cathode materials reduces the competitiveness of AIBs in practical applications. Herein, a conversion‐type FeF3‐expanded graphite (EG) composite is synthesized as a novel cathode material for AIBs with good conductivity and cycle stability. Combined with the introduction of a single‐wall carbon nanotube modified separator, the shuttle effect of the intermediate product, FeCl2, is significantly restrained. Moreover, enhanced coulombic efficiency and reversible capacity are achieved. The AIB exhibits a satisfying reversible specific capacity of 266 mAh g−1 at 60 mA g−1 after 200 cycles, and good Coulombic efficiency of nearly 100% after 400 cycles at a current density of 100 mA g−1. Ex situ X‐ray diffraction and X‐ray photoelectron spectroscopy are applied to explore the energy storage mechanism of FeF3 in AIBs. The results reveal that the intercalation of Al3+ species and the reduction of Fe3+ species occurrs in the discharge process. These findings are meaningful for the fundamental understanding of the FeF3 cathode for AIBs and provide unprecedented insight into novel conversion type cathode materials for AIBs. A conversion‐type FeF3@expanded graphite (EG) composite is designed in this work, which realizes the Fe3+ to Fe redox reaction and exhibits high reversible capacity. The formation of CF bonds between FeF3 and EG not only enhances the electronic conductivity, but also buffers the volume change. In addition, a modified single‐wall carbon nanotube separator improves the suppression of the shuttle effect.