High-efficient and long-cycle air cathodes are crucial for the development of rechargeable zinc-air batteries (ZABs). Herein, we develop a strategy of micro-spherical cobalt-doped Fe₅(PO₄)₄(OH)₃·H₂O (Co-FPOH), synthesized by a novel water-oil two-phase hydrothermal method, which was used as ORR/OER bifunctional electrocatalyst for ZABs. The change of local electronic distribution is identified by doping of Co into Fe₅(PO₄)₄(OH)₃·H₂O (FPOH), effectively improving the electrocatalytic performance of the resulted Co-FPOH. The OER overpotential of Co-FPOH (290 mV) far outperforms state-of-the-art RuO₂ (350 mV); the ORR catalytic reaction of Co-FPOH is near 4e^-, almost reaching the theoretical value of Pt/C (n = 4.00). The ZAB assembled with Co-FPOH as an air electrode exhibits an ultralong cycling lifetime of 450 h at 5 mA cm⁻², a super high peak power density of 167.8 Wh cm⁻², a high open circuit voltage of about 1.42 V and a large discharge specific capacity of 817 mAh g_Zn⁻¹ at 10 mA cm⁻². The proposed Co-FPOH is expected to outperform precious metal electrocatalysts as a potential bifunctional electrocatalyst for advanced ZABs. Also, this work offers a novel strategy to synthesize excellent bifunctional electrocatalysts for this kind of energy-related electrocatalytic reactions.

高效、长循环的空气阴极对于可充电锌空气电池（ZABs）的发展至关重要。在此，我们开发了一种通过新型水油两相水热法合成的微球型钴掺杂 Fe ₅ (PO ₄ ) ₄ (OH) ₃ ·H ₂ O (Co-FPOH)作为 ZAB 的 ORR/OER 双功能电催化剂。通过将 Co 掺杂到 Fe ₅ (PO ₄ ) ₄ (OH) ₃ ·H _{2 中}来识别局部电子分布的变化O (FPOH)，有效提高了所得 Co-FPOH 的电催化性能。Co-FPOH (290 mV) 的 OER 过电位远远优于最先进的 RuO ₂ (350 mV)；Co-FPOH的ORR催化反应接近4e ^-，几乎达到了Pt/C的理论值（n  = 4.00）。以 Co-FPOH 作为空气电极组装的 ZAB 在 5 mA cm ^{-2 下}具有 450 h 的超长循环寿命、167.8 Wh cm ^-2的超高峰值功率密度、约 1.42 V 的高开路电压和817 mAh g _Zn ^-1在 10 mA cm ^{-2 下的}大放电比容量. 所提出的 Co-FPOH 作为高级 ZAB 的潜在双功能电催化剂，有望优于贵金属电催化剂。此外，这项工作提供了一种新的策略来合成用于这种与能量相关的电催化反应的优良双功能电催化剂。