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The utilization of hydrazine in aiding water electrolysis presents a promising avenue for achieving highly efficient hydrogen production through energy conversion. Herein, bifunctional electrocatalyst of urchin‐like iron, nickle‐codoped cobalt phosphide supported on Ni foam (FeNi‐CoP/NF) is reported. Benefitting from the combined electronic structure and lattice strain engineering by Fe and Ni‐ codoping, the hydrazine‐assisted seawater electrolysis assembled with FeNi‐CoP/NF as both electrodes can achieve an industrial‐level current density of 1.5 A cm−2 at a record‐setting voltage of 163 mV at 70 °C and sustain stable operation for hundreds of hours in seawater environment. The existence of a potential coincidence region lends credibility to the feasibility of implementing self‐activated hydrazine‐assisted seawater electrolysis. Based on theoretical calculations, the separate and synergistic effects of electronic structure and lattice strain engineering are investigated and an integrated illustration of these two strategies on enhancing hydrogen evolution and hydrazine oxidation activity is provided. Moreover, an innovative multi‐powered hydrogen generation system featuring a direct hydrazine fuel cell, rechargeable Zn‐hydrazine battery, and hydrazine‐assisted seawater electrolysis is proposed, underscoring the unique advantages of hydrazine oxidation reaction and its prospective contribution to electrochemical energy conversion technologies powered by sustainable sources. [ABSTRACT FROM AUTHOR]

The development and utilization of electrochemical energy conversion and storage devices can maximize intermittent renewable energy and balance environmental issues. Aqueous metal‐redox bicatalyst batteries, incorporating value‐added electro‐reduction reactions during discharge process at the cathode, are considered a particularly attractive alternative for simultaneous electricity generation and valuable chemical production. In this review, for the first time, a holistic and subtle description of value‐added metal‐redox bicatalyst batteries is made, focusing on recent efforts to optimize the energy conversion/chemical production‐involved cathodic discharging reactions, including CO2 reduction reaction (CO2RR), nitrogen reduction reaction (NRR), nitric oxide reduction reaction (NORR), nitrate reduction reaction (NO3−RR), nitrite reduction reaction (NO2−RR), hydrogen evolution reaction (HER), and acetylene reduction reaction (ARR). A macroscopic understanding of design principles in terms of anodes, cathodes, and reaction parameters is provided. Some mechanism explorations, feasibility analyses, technoeconomic assessments, device combinations, and associated comparisons are involved to deepen the understanding of different systems and evaluate their application prospects. Perspectives on and opportunities for future research directions are also outlined. [ABSTRACT FROM AUTHOR]