Aqueous aluminum-ion batteries (AAIBs) hold significant promise for large-scale energy storage due to the high volumetric and gravimetric capacities of metallic aluminum, as well as its abundance and environmental benignity. However, their practical implementation is hindered by the low redox potential of aluminum, parasitic hydrogen evolution, and the formation of passivation layers at the anode–electrolyte interface. Aluminum alloys have emerged as promising anode candidates, offering enhanced corrosion resistance, reduced passivation and improved interfacial stability, enabling more reversible and stable electrochemical performance. Nevertheless, alloy anodes still face suboptimal cycling stability, primarily due to large volumetric and structural changes during charge–discharge processes, which induce mechanical degradation and exacerbate interfacial side reactions. This review presents a comprehensive overview of the interfacial chemistry of aluminum alloy anodes for AAIBs. It first outlines the fundamental energy storage mechanisms and summarizes the key issues of alloy-based anodes. Afterwards, the classification and physicochemical properties of different aluminum alloys are discussed, with emphasis on interfacial characteristics and mechanistic insights into their electrochemical behavior. Critical challenges are further analyzed, and rational design strategies are proposed to enhance performance. Finally, future directions of interfacial engineering are outlined to guide the development of aluminum alloy anodes for next-generation AAIBs.
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