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Abstract Aqueous trivalent metal batteries represent a compelling candidate for energy storage due to the intriguing three‐electron transfer reaction and the distinct properties of trivalent cations. However, little research progress has been achieved with trivalent batteries due to the inappropriate redox potentials and drastic ion hydrolysis side reactions. Herein, the appealing yet underrepresented trivalent indium is selected as an advanced metal choice and the crucial effect of substrate on its plating mechanism is revealed. When copper foil is used, an indiophilic indium‐copper alloy interface can be formed in situ upon plating, exhibiting favorable binding energies and low diffusion energy barriers for indium atoms. Consequently, a planar, smooth, and dense indium metal layer is uniformly deposited on the copper substrate, leading to outstanding plating efficiency (99.8–99.9%) and an exceedingly long lifespan (6.4–7.4 months). The plated indium anode is further paired with a high‐mass‐loading Prussian blue cathode (2 mAh cm⁻²), and the full cell (negative/positive electrode capacity, N/P = 2.5) delivers an excellent cycling life of 1000 cycles with 72% retention. This work represents a significant advancement in the development of high‐performance trivalent metal batteries. 

Aqueous sodium-ion batteries (ASIBs) represent a promising battery technology for stationary energy storage, due to their attractive merits of low cost, high abundance, and inherent safety. Recently, a variety of advanced cathode, anode, and electrolyte materials have been developed for ASIBs, which not only enhance our fundamental understanding of the Na insertion mechanism, but also facilitate the research and development of practical ASIB systems. Among these electrode materials, iron-based materials are of particular importance because of the high abundance, low price, and low toxicity of Fe elements. However, to our knowledge, there are no review papers that specifically discuss the properties of Fe-based materials for ASIBs yet. In this review, we present the recent research progress on Fe-based cathode/anode materials, which include polyanionic compounds, Prussian blue, oxides, carbides, and selenides. We also discuss the research efforts to build Fe-based ASIB full cells. Lastly, we share our perspectives on the key challenges that need to be addressed and suggest alternative directions for aqueous Na-ion batteries. We hope this review paper can promote more research efforts on the development of low-cost and low-toxicity materials for aqueous battery applications.