Benefiting from the advantageous features of high safety, abundant reserves, low cost, and high energy density, aqueous Zn‐based rechargeable batteries (AZBs) have received extensive attention as promising candidates for energy storage. To achieve high‐performance AZBs with high reversibility and energy density, great efforts have been devoted to overcoming their drawbacks by focusing on the modification of electrode materials and electrolytes. Based on different cathode materials and aqueous electrolytes, the development of aqueous AZBs with different redox mechanisms are discussed in this review, including insertion/extraction chemistries (e.g., Zn²⁺, alkali metal ion, H⁺, NH₄⁺, and so forth) dissolution/deposition reactions (e.g., MnO₂/Mn²⁺), redox couples in flow batteries (e.g., I₃⁻/3I⁻, Br₂/Br⁻, and so forth), oxygen electrochemistry (e.g., O₂/OH⁻, O₂/O₂²⁻), and carbon dioxide electrochemistry (e.g., CO₂/CO, CO₂/HCOOH). In particular, the basic reaction mechanisms, issues with the Zn electrode, aqueous electrolytes, and cathode materials as well as their design strategies are systematically reviewed. Finally, the remaining challenges faced by AZBs are summarized, and perspectives for further investigations are proposed.

Screening and constructing low cost, highly efficient and robust electrocatalysts with high oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity is crucial for rechargeable metal–air batteries. Metal phosphides coupled with heteroatom doped carbon are promising candidates for oxygen electrodes. In this work, we demonstrate a facile strategy to synthesize cobalt phosphide anchored heteroatom (N,P) co-doped porous carbon (CoP/NP-HPC) through a one-step pyrolysis of bimetal–organic frameworks with a simple in situ phosphorization process. In alkaline solution, the obtained CoP/NP-HPC catalyst exhibits high bifunctional catalytic activity toward ORR and OER, comparable to commercial 20% Pt/C or even better, which is attributed to the synergistic effect between the CoP active sites and N,P co-doped carbon, and the porous framework as a channel benefiting the diffusion of reaction species. Notably, a rechargeable Zn–air battery with CoP/NP-HPC as the cathode electrocatalyst delivers a high power density of 186 mW cm⁻², as well as good long-term charge/discharge cyclic stability, outperforming 20% Pt/C. The hybrid catalyst of CoP anchored heteroatom doped carbon provides a possibility and an opportunity to promote the development of low-cost and highly efficient bifunctional catalysts for ORR and OER in applications of metal–air batteries.

Triple-atom catalysts exhibit moderate adsorption energy for intermediate species, enabling the optimal performance of the CO₂ electrocatalytic reduction reaction.