Flexible and aqueous Zn–air batteries constitute promising next-generation energy storage devices to meet the growing demand for a safe and stable energy supply for flexible displays, wearable electronics, and implantable medical devices. However, their practical applications are severely hindered by the sluggish kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) at the air cathode. Herein, a porphyrin covalent organic framework (POF) was innovatively designed and applied as a cathode electrocatalyst for flexible Zn–air batteries. Porphyrin active sites were periodically constructed into well-defined two-dimensional (2D) frameworks precisely controlled at the atomic level, and carbon nanotubes (CNTs) served as scaffolds for further morphology regulation. Interwoven into a free-standing, robust, and flexible film, the as-fabricated CNT@POF hybrid demonstrates impressive performance in rechargeable liquid and flexible all-solid-state Zn–air batteries. Specifically, the liquid Zn–air battery with the CNT@POF cathode exhibits a small voltage gap of 0.71 V and outstanding stability for 200 cycles, even better than the noble-metal-based cathode. Flexible all-solid-state Zn–air batteries demonstrate a high energy efficiency of 61.6% at 1.0 mA cm⁻² and the flexibility to stably light a red light-emitting diode (LED, 2.0 V) when bent to different degrees. This contribution demonstrates versatile and ingenious strategies for the multiscale regulation of advanced materials for energy electrocatalysis and thereby facilitates their applications in flexible and safe energy storage and conversion.

中文翻译：

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柔性锌空气电池的卟啉共价有机骨架阴极†

柔性和水性Zn-空气电池构成了有希望的下一代储能设备，可以满足对柔性显示器，可穿戴电子设备和植入式医疗设备对安全稳定的能源供应不断增长的需求。但是，它们的实际应用由于空气阴极处的氧还原反应（ORR）和氧释放反应（OER）的动力学缓慢而受到严重阻碍。在此，创新设计了卟啉共价有机骨架（POF），并将其用作柔性Zn-空气电池的阴极电催化剂。卟啉活性位点被周期性地构建为在原子水平上精确控制的定义明确的二维（2D）框架，并且碳纳米管（CNT）充当了进一步形态调节的支架。交织成独立的，坚固的，CNT @ POF复合材料和柔性薄膜在可充电液体和柔性全固态Zn-空气电池中显示出令人印象深刻的性能。特别是，带有CNT @ POF阴极的液态Zn-空气电池表现出0.71 V的小电压间隙，并具有200次循环的出色稳定性，甚至比贵金属基阴极还要好。柔性全固态Zn-空气电池在1.0 mA cm处显示出61.6％的高能效^-2和弯曲不同程度时稳定点亮红色发光二极管（LED，2.0 V）的灵活性。这一贡献展示了用于能量电催化高级材料的多尺度调节的通用而巧妙的策略，从而促进了它们在灵活，安全的能量存储和转换中的应用。