Aqueous zinc–manganese batteries with low cost, reliable safety, and considerable energy density, show promise for grid‐scale storage. Their durable operation is highly dependent on the reversibility and stability of both electrode interfaces, which is limited by the different requirements of the interfaces of manganese‐based cathodes and zinc anodes. Here, a quasi‐decoupled solid–liquid hybrid electrolyte is proposed, which demonstrates good compatibility and high reversibility for both interfaces with different electrolyte environments, showing quasi‐decoupling characteristics. Such a hybrid electrolyte can endow the anode interface with abundant favorable nucleation sites for achieving uniform zinc platting/stripping, as well as limit the presence of free H2O molecules, to suppress side‐reactions. This electrolyte is also adapted to a reversible and stable MnO2/Mn2+ manganese deposition/dissolution reaction at the cathode interface by restricting OH−/H+ ion diffusion, preventing formation of irreversible electrochemically inert MnOOH. As a result, the quasi‐decoupled solid–liquid hybrid electrolyte enables Zn||Zn cycling for more than 500 h, and a specific capacity of a Zn||α‐MnO2 battery up to 348 mAh g−1 at 0.2 A g−1. It also allows 87% capacity retention after 500 cycles at 0.5 A g−1. This work provides a new insight into electrolyte design that focuses on the different requirements of differing electrode interfaces.

Material with layered structure has been widely adopted as ion(s)−(de)intercalated type cathode for zinc ion battery but suffered from limited operating voltage of restricted redox couple. While I−/I2 transition with...

Zinc‐metal batteries (ZMBs) are promising for large‐scale energy storage devices due to their intrinsically safe, low‐cost and environmentally friendly nature. ZMBs with vanadium‐based cathodes have exhibited excellent performance, however, many side reactions due to the presence of innumerable water molecules in aqueous electrolyte hinder their commercialization. Herein, high‐proportioned polyethylene glycol was introduced as solvent to form an aqueous/organic hybrid electrolyte, which limits the activity of free water molecules and lowers the risk of side reactions, such as cathode dissolution, zinc dendrites and H2 evolution. As a result, a good reversible zinc plating/stripping over 3000 h for zinc anode and an excellent cycle stability with 96 % retention after 50 cycles at low current density of 0.1 A g−1 for vanadium‐based cathode were obtained, respectively. Importantly, to simulate the stability in actual application environment, a test mode at low current density under both continuous and intermittent electrochemical charge/discharge was conducted, which further demonstrated the superiority of this hybrid electrolyte. Finally, as a practical illustration, the pouch cells of 3 cm×3 cm exhibit a high capacity of 300 mAh g−1 at 0.1 A g−1 with a good retention of 81.7 % after 200 cycles, and even up to 500 cycles at 0.5 A g−1. This work is expected to provide new opportunities for high‐performance hybrid electrolyte for the practical ZMBs.