From Carrier Behavior to Cathode Design: Toward High‐Performance Aluminum Batteries

ABSTRACT This review systematically summarizes recent advances in cathode materials for aluminum batteries (ABs), emphasizing the critical influence of carrier properties on electrode performance. Focusing on carrier properties, including ionic size, valence, charge density, and coordination environment, we analyze their transport kinetics, interfacial reactions, and energy storage mechanisms across different cathode systems, including Al 3+ , AlCl 4 − , AlCl 2 + , as well as the synergistic behavior of multiple carriers. We identify intrinsic carrier characteristics, solvation/desolvation dynamics, and the electrode/electrolyte interface as the primary factors governing battery performance. Furthermore, the review delineates the constraints of cathode materials in achieving high capacity, fast kinetics, and long‐term cycling stability. An integrated framework for understanding carrier behavior and energy storage mechanisms is established, accompanied by a systematic classification of cathode materials, including inorganic, Prussian blue, and organic compounds, together with their corresponding optimization strategies. Finally, universal design principles for structural engineering, electronic structure modulation, defect/doping, and interface engineering are proposed. More importantly, this review establishes a carrier‐centered framework that systematically links carrier chemistry, charge storage mechanisms, and cathode design principles, thereby providing a unified mechanistic perspective for the rational development of next‐generation high‐performance ABs.