Huang Hongrui, Liang Qianqian, Guo Huajun, Wang Zhixing, Yan Guochun, Wu Feixiang, Wang Jiexi
Engineering Research Center of the Ministry of Education for Advanced Battery Materials, Hunan Provincial Key Laboratory of Value-added Metallurgy, School of Metallurgy and Environment, Central South University, Changsha, 410083, P. R. China.
Small. 2024 Jun;20(23):e2310318. doi: 10.1002/smll.202310318. Epub 2024 Jan 6.
Low-cost and high-efficiency non-precious metal-based oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) bifunctional catalysts are the key to promoting the commercial application of metal-air batteries. Herein, a highly efficient catalyst of FeCo alloy anchoring on the nitrogen-doped porous carbon hollow sphere (FeCo/N-C) is intelligently designed by spray pyrolysis (SP). The zinc in the SP-derived metal oxides and metal-organic framework volatilize at high temperature to construct a hierarchical porous structure with abundant defects and fully exposes the FeCo nanoparticles which uniformly anchor on the carbon substrate. In this structure, the coexistence of FeCo alloy and binary metal active sites (Fe-N/Co-N) guarantees the FeCo/N-C catalyst exhibiting an excellent half-wave potential (E ═ 0.84 V) superior to 20% Pt/C for ORR and a suppressed overpotential (280 mV) than RuO for OER. Assembled rechargeable Zn-air battery (RZAB) demonstrates a promising specific capacity of 807.02 mAh g, peak power density of 159.08 mW cm and durability without electrolyte circulation (550 h). This work proposes the design concept of utilizing an oxide core to in situ consume the porous carbon shell for anchoring metal active sites and construct defects, which benefits from spray pyrolysis in achieving precise control of the alloy structure and mass preparation.
低成本、高效率的非贵金属基氧还原反应(ORR)/析氧反应(OER)双功能催化剂是推动金属空气电池商业应用的关键。在此,通过喷雾热解(SP)智能设计了一种锚定在氮掺杂多孔碳空心球上的高效FeCo合金催化剂(FeCo/N-C)。喷雾热解衍生的金属氧化物和金属有机框架中的锌在高温下挥发,构建了具有丰富缺陷的分级多孔结构,并充分暴露了均匀锚定在碳基底上的FeCo纳米颗粒。在这种结构中,FeCo合金和二元金属活性位点(Fe-N/Co-N)的共存保证了FeCo/N-C催化剂在ORR中表现出优于20% Pt/C的优异半波电位(E = 0.84 V),在OER中比RuO具有更低的过电位(280 mV)。组装的可充电锌空气电池(RZAB)展示了807.02 mAh g的有前景的比容量、159.08 mW cm的峰值功率密度以及无需电解液循环的耐久性(550 h)。这项工作提出了利用氧化物核原位消耗多孔碳壳以锚定金属活性位点并构建缺陷的设计概念,这得益于喷雾热解在实现合金结构精确控制和大规模制备方面的优势。