Rechargeable zinc-air batteries (ZABs) stand out among next-generation battery technologies due to their high energy density and high safety but suffer from electrochemical irreversibility. Herein, we report a hybrid ZAB with a long lifespan and high working voltage; it uses a neutral anolyte, an acidic catholyte, and a proton-shuttle-shielding dual-hydrophobic membrane to isolate the two electrolytes. The hybrid ZAB operates through the stable electrochemical plating and stripping of zinc (Zn) in a neutral anolyte and a high-voltage O₂ redox reaction in acidic catholyte. The designed proton-shuttle-shielding dual-hydrophobic membrane selectively transports hydrophobic bis(trifluoromethylsulfonyl)imide anions (TFSI⁻) and effectively avoids the crossover of protons. As a result, the hybrid ZAB exhibits a high working voltage (1.50 V) and stable operation (up to 2,000.0 h) in ambient air. This strategy not only overcomes the severe irreversibility of conventional ZABs but also promotes development of electrolyte-decoupled systems.

可充电锌空气电池 (ZAB) 因其高能量密度和高安全性而在下一代电池技术中脱颖而出，但存在电化学不可逆性。在此，我们报告了一种具有长寿命和高工作电压的混合 ZAB；它使用中性阳极液、酸性阴极液和质子穿梭屏蔽双疏水膜来隔离两种电解质。混合 ZAB 通过在中性阳极液中稳定的电化学电镀和剥离锌 (Zn) 以及在酸性阴极液中进行高压 O _{2氧化还原反应来运行。}设计的质子穿梭屏蔽双疏水膜选择性地传输疏水双（三氟甲基磺酰基）亚胺阴离子（TFSI ^-) 并有效地避免了质子的交叉。因此，混合 ZAB 在环境空气中表现出高工作电压 (1.50 V) 和稳定运行 (高达 2,000.0 h)。该策略不仅克服了传统 ZAB 的严重不可逆性，而且促进了电解质解耦系统的发展。