原子级铁锚定氮掺杂石墨烯的双功能氧电催化性能

doi:10.15541/jim20250519

摘要/Abstract

摘要： 随着对高效环保储能系统需求的日益增长,锌空电池因其高能量密度、低成本及环境友好等特性,成为极具前景的能源存储装置。然而,空气阴极上缓慢的氧还原(ORR)和析氧反应(OER)动力学制约了电池性能的进一步提升,故开发高性能、低成本的双功能氧电催化剂具有重要意义。本实验通过球磨辅助热解法,制备了Fe单原子/团簇锚定石墨烯杂化催化剂(Fe-N/Gra)。通过调控前驱体金属酞菁与石墨烯的比例,获得了系列Fe-N/Gra材料,并考察了其氧双功能电催化性能。研究结果表明,不同金属酞菁前驱体量对催化剂性能具有较大的影响。当酞菁铁载量为0.02 g时,所得Fe-N/Gra-0.02展现出最佳的ORR和OER催化活性：其ORR半波电位高达0.911 V,OER在10 mA•cm^-2下的过电位为610 mV。以该催化剂作为空气电极组装的可充式锌空电池,最大功率密度达315 mW•cm^-2,在10 mA•cm^-2电流密度下可稳定放电220 h。Fe-N/Gra-0.02良好的双功能氧催化活性主要归因于原子级分散FeN_x活性位和载体石墨烯的高导电性,另外高负载量催化剂中活性位的团聚不利于展现其高效催化活性。本研究为高性能非贵金属双功能催化剂的可控制备及锌空电池的应用提供了实验依据。

关键词: 铁锚定氮掺杂石墨烯, 单原子/团簇, 氧还原反应, 析氧反应, 锌空电池

Abstract: With the growing demand for efficient and environmentally friendly energy storage systems, zinc-air batteries have emerged as highly promising energy storage devices due to their high energy density, low cost, and environmental friendliness. The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), which suffer from sluggish kinetics, are critical factors limiting battery performance. Therefore, the development of high-performance and low-cost bifunctional oxygen electrocatalysts is of great significance. In this work, Fe single atoms / clusters anchored graphene hybrid catalysts (Fe-N/Gra) were prepared via a ball-milling assisted pyrolysis method. A series of Fe-N/Gra catalysts were obtained by adjusting the mass ratio of the metal phthalocyanine precursor to graphene, and their bifunctional oxygen electrocatalytic performances were systematically investigated. The results demonstrate that the loading amount of different metal phthalocyanine precursors exerts a significant influence on the catalytic performance of the catalysts. When the loading amount of iron phthalocyanine was 0.02 g, the resulting Fe-N/Gra-0.02 catalyst exhibited the optimal bifunctional catalytic activity for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER): its ORR half-wave potential reached as high as 0.911 V, and the OER overpotential was 610 mV at a current density of 10 mA•cm^-2. The rechargeable zinc-air batteries assembled with this catalyst as the air electrode achieved a maximum power density of 315 mW•cm^-2 and could sustain stable discharge for 220 h at 10 mA•cm^-2. The excellent bifunctional oxygen catalytic activity of Fe-N/Gra-0.02 is mainly attributed to the atomically dispersed FeN_x active sites and the high electrical conductivity of graphene support. In addition, the agglomeration of active sites in the catalysts with excessive loading amounts is detrimental to the manifestation of their high-efficiency catalytic activity. This work provides an experimental basis for the controllable preparation of high-performance non-noble metal bifunctional oxygen catalysts and their practical applications in rechargeable zinc-air batteries.

Key words: iron-anchored nitrogen-doped graphene, single-atom/cluster, oxygen reduction reaction, oxygen evolution reaction, Zn-air battery

中图分类号:

TB383

汪加辉, 刘晶晶, 邱毅, 王永霞, 崔香枝. 原子级铁锚定氮掺杂石墨烯的双功能氧电催化性能[J]. 无机材料学报, DOI: 10.15541/jim20250519.

WANG Jiahui, LIU Jingjing, QIU Yi, WANG Yongxia, CUI Xiangzhi. Bifunctional Oxygen Electrocatalytic Performance of Atomically Dispersed Fe anchored on N doped Graphene[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250519.

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