氮掺杂碳纳米管包覆Fe0.64Ni0.36@Fe3NiN核壳结构用于高稳定锌-空气电池

doi:10.3866/PKU.WHXB202304021

摘要/Abstract

摘要：

可逆锌-空气电池因其高功率密度和环境友好性而得到了广泛研究。然而，氧还原反应(ORR)和氧析出反应(OER)的缓慢动力学限制了其实际应用。迄今为止，二氧化铱和二氧化钌被认为是氧析出反应的最佳电催化剂，同时铂碳被认为是最有效的氧还原反应的电催化剂。然而，由于Pt、Ir和Ru的天然丰度低、成本高的原因，它们在ZABs中的实际应用严格受限。因此，探索低成本和高性能的双功能催化剂对促进可充电锌-空气电池的发展至关重要。具有高导电性、低氧还原反应能垒的过渡金属合金可作为有潜力的氧还原电催化剂。为提高过渡金属合金催化剂的双功能催化活性，可构筑过渡金属合金@过渡金属氮化物的核壳结构。在此，我们设计了一种氮掺杂碳纳米管包覆Fe_0.64Ni_0.36@Fe₃NiN核壳结构(Fe_0.64Ni_0.36@Fe₃NiN/NCNT)的双功能电催化剂，其具有高效的双功能催化活性。核壳结构可以为ORR/OER产生更多的活性点。Fe_0.64Ni_0.36核具有高导电性，有助于电荷转移。Fe₃NiN壳有助于提升催化剂的OER性能。氮掺杂碳纳米管不仅能够有效增强传质效应和内部电荷传递，还可以提升其电化学活性表面积。此外，具有高抗腐蚀性能的Fe₃NiN外壳可以有效地保护Fe_0.64Ni_0.36内核，从而提高了电化学过程中催化剂的稳定性。氮掺杂碳纳米管对Fe_0.64Ni_0.36@Fe₃NiN核壳结构也具有一定的保护作用，因此Fe_0.64Ni_0.36@Fe₃NiN/NCNT表现出优异的稳定性。Fe_0.64Ni_0.36@Fe₃NiN/NCNT催化剂表现出优异的双功能氧电催化性能，获得ORR的半波电位为0.88 V，在10 mA∙cm⁻²时的OER过电位为380 mV，以及高电化学稳定性(8 h后电流密度剩余92.8%)。此外，与基于Pt/C + IrO₂ (155 mW∙cm⁻²)和Fe_0.64Ni_0.36/NCNT (89 mW∙cm⁻²)的锌-空气电池相比，基于Fe_0.64Ni_0.36@Fe₃NiN/NCNT的锌-空气电池展现出更高的功率密度(214 mW∙cm⁻²)，提供781 mAh∙g⁻¹的高容量，并展现出了超长的循环稳定性(循环寿命超过1100 h)。我们相信这项工作将对于新型催化剂设计有所启发，从而实现高度稳定和高效的锌-空气电池。

关键词: 双功能电催化剂, Fe₃NiN, 核壳结构, 锌-空气电池, 长循环寿命

Abstract:

Rechargeable zinc-air batteries (ZABs) have been extensively investigated owing to their high power density and environmental friendliness. However, the slow kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) processes limit their practical application. Currently, IrO₂ and RuO₂ are considered the optimal OER electrocatalysts, and Pt/C is the most effective ORR electrocatalyst. However, the practical application of Pt, Ir, and Ru in ZABs is severely limited owing to their low natural abundance and high cost. Therefore, the fabrication of inexpensive and high-performance bifunctional catalysts is essential for the development of rechargeable ZABs. Transition-metal alloys have a high electrical conductivity and low energy barrier for the reaction of oxygen, and thus they are considered promising ORR electrocatalysts. Transition-metal nitride-transition-metal alloy core-shell nanostructures can be fabricated to improve the bifunctional electrocatalytic activity. In this study, a bifunctional electrocatalyst with Fe_0.64Ni_0.36@Fe₃NiN core-shell structures encapsulated in N-doped carbon nanotubes (Fe_0.64Ni_0.36@Fe₃NiN/NCNT) was designed for highly efficient rechargeable ZABs. Fe_0.64Ni_0.36@Fe₃NiN/NCNT was synthesized by pyrolyzing the nickel-iron-layered double hydroxide (NiFe-LDH) precursor, followed by ammonia etching of the Fe_0.64Ni_0.36 alloy. The core-shell structure produced more ORR/OER active sites. The Fe_0.64Ni_0.36 core exhibited high electrical conductivity, which facilitates charge transfer. The Fe₃NiN shell enhanced the OER performance and improved the bifunctional performance. Moreover, the NCNT structures not only efficiently enhanced the mass transfer efficiency and intrinsic electrical conductivity, but also provided a large electrochemical active surface area. The high anticorrosion property of the Fe₃NiN shell effectively protected the Fe_0.64Ni_0.36 core, which consequently enhanced electrocatalyst stability during the electrochemical processes. The protective carbon layer and the superior chemical stability of the Fe₃NiN shell resulted in the ultrahigh stability of Fe_0.64Ni_0.36@Fe₃NiN/NCNT. The catalyst exhibited an excellent bifunctional oxygen electrocatalytic performance, with a half-wave potential of 0.88 V for the ORR and low OER overpotential of 380 mV at 10 mA∙cm⁻². Moreover, the catalyst exhibited electrochemical stability (92.8% current retention after 8 h). In addition, the Fe_0.64Ni_0.36@Fe₃NiN/NCNT-based ZAB exhibited a higher peak power density (214 mW·cm⁻²) than the ZABs based on Pt/C+IrO₂ (155 mW·cm⁻²) and Fe_0.64Ni_0.36/NCNT (89 mW·cm⁻²). Moreover, the Fe_0.64Ni_0.36@Fe₃NiN/NCNT-based ZAB delivered a high capacity of 781 mAh·g⁻¹, while the ZABs based on Fe_0.64Ni_0.36/NCNT and Pt/C+IrO₂ reached capacities of 688 and 739 mAh·g⁻¹, respectively. Furthermore, the Fe_0.64Ni_0.36@Fe₃NiN/NCNT-based ZAB exhibited ultralong cycling stability (cycle life > 1100 h), which exceeded those of Pt/C (50 h) and Fe_0.64Ni_0.36/NCNT (450 h). We propose that this study will facilitate the design of novel catalysts for highly stable and efficient ZABs.

Key words: Bifunctional electrocatalyst, Fe₃NiN, Core-shell structure, Zinc-air battery, Ultra-long cycle stability

蒲晨, 邓代洁, 李赫楠, 徐丽. 氮掺杂碳纳米管包覆Fe_0.64Ni_0.36@Fe₃NiN核壳结构用于高稳定锌-空气电池[J]. 物理化学学报, 2024, 40(2), 2304021. doi: 10.3866/PKU.WHXB202304021

Chen Pu, Daijie Deng, Henan Li, Li Xu. Fe_0.64Ni_0.36@Fe₃NiN Core-Shell Nanostructure Encapsulated in N-Doped Carbon Nanotubes for Rechargeable Zinc-Air Batteries with Ultralong Cycle Stability[J]. Acta Phys. -Chim. Sin. 2024, 40(2), 2304021. doi: 10.3866/PKU.WHXB202304021

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202304021

https://www.whxb.pku.edu.cn/CN/Y2024/V40/I2/2304021

图/表 4

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氮掺杂碳纳米管包覆Fe_0.64Ni_0.36@Fe₃NiN核壳结构用于高稳定锌-空气电池

Fe_0.64Ni_0.36@Fe₃NiN Core-Shell Nanostructure Encapsulated in N-Doped Carbon Nanotubes for Rechargeable Zinc-Air Batteries with Ultralong Cycle Stability

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