Li Yifan, Huang Aijian, Zhou Lingxi, Li Bohan, Zheng Muyun, Zhuang Zewen, Chen Chang, Chen Chen, Kang Feiyu, Lv Ruitao
State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing, China.
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Canada.
Nat Commun. 2024 Sep 27;15(1):8365. doi: 10.1038/s41467-024-52494-0.
Developing highly active and durable air cathode catalysts is crucial yet challenging for rechargeable zinc-air batteries. Herein, a size-adjustable, flexible, and self-standing carbon membrane catalyst encapsulating adjacent Cu/Na dual-atom sites is prepared using a solution blow spinning technique combined with a pyrolysis strategy. The intrinsic activity of the Cu-N site is boosted by the neighboring Na-containing functional group, which enhances O adsorption and optimizes the rate-determining step of O activation (*O → *OOH) during the oxygen reduction reaction process. Meanwhile, the Cu-N sites are encapsulated within carbon nanofibers and anchored by the carbon matrix to form a C-Cu-N configuration, thereby reinforcing the stability of the Cu centers. Moreover, the introduction of Na-containing functional groups on the carbon atoms significantly reduces the positive charge on their outer shell C atoms, rendering the carbon skeletons less susceptible to corrosion by oxygen species and further preventing the dissolution of Cu centers. Under these multi-type regulations, the zinc-air battery with Cu/Na-carbon membrane catalyst as the air cathode demonstrates long-term discharge/charge cycle stability of over 5000 h. This considerable stability improvement represents a critical step towards developing Cu-N active sites modified with the neighboring main-group metal-containing functional groups to overcome the durability barriers of zinc-air batteries for future practical applications.
开发高活性和耐用的空气阴极催化剂对于可充电锌空气电池至关重要，但具有挑战性。在此，采用溶液吹纺技术结合热解策略制备了一种包裹相邻Cu/Na双原子位点的尺寸可调、柔性且自支撑的碳膜催化剂。相邻的含Na官能团提高了Cu-N位点的本征活性，增强了O吸附，并优化了氧还原反应过程中O活化的速率决定步骤（*O → *OOH）。同时，Cu-N位点被封装在碳纳米纤维内并由碳基体锚定，形成C-Cu-N构型，从而增强了Cu中心的稳定性。此外，在碳原子上引入含Na官能团显著降低了其外壳C原子上的正电荷，使碳骨架更不易受到氧物种的腐蚀，并进一步防止Cu中心的溶解。在这些多类型调控下，以Cu/Na-碳膜催化剂为空气阴极的锌空气电池表现出超过5000小时的长期充放电循环稳定性。这种显著的稳定性提升是朝着开发用相邻主族金属官能团修饰的Cu-N活性位点迈出的关键一步，以克服锌空气电池在未来实际应用中的耐久性障碍。
