铋牺牲法制备石墨烯负载Fe-N单原子位点增效氧还原催化和锌-空气电池性能

doi:10.1016/S1872-2067(24)60002-1

催化学报 ›› 2024, Vol. 59: 272-281.DOI: 10.1016/S1872-2067(24)60002-1

铋牺牲法制备石墨烯负载Fe-N单原子位点增效氧还原催化和锌-空气电池性能

杨志远^a, 张燕^a, 肖娟定^a, 王俊英^b^,^*(), 王俊中^a^,^*()

^a安徽大学物质科学与信息技术研究院, 安徽石墨烯碳纤维材料工程研究中心, 安徽合肥 230601
^b中国科学院山西煤炭化学研究所, 炭材料山西省重点实验室, 山西太原 030001

收稿日期:2023-12-17 接受日期:2024-02-14 出版日期:2024-04-18 发布日期:2024-04-15
通讯作者: *电子信箱: wangjz@ahu.edu.cn (王俊中), wangjy@sxicc.ac.cn (王俊英).
基金资助:
国家自然科学基金(22279001);国家自然科学基金(22179138);山西省自然科学基金(20210302123005);安徽省重大科技专项项目(2022e03020007)

Enhancing oxygen reduction of Fe-N-C active sites onto graphene via bismuth sacrifice for Zn-air batteries

Zhiyuan Yang^a, Yan Zhang^a, Juanding Xiao^a, Junying Wang^b^,^*(), Junzhong Wang^a^,^*()

^aInstitutes of Physical Science and Information Technology, Anhui Graphene Carbon Fiber Materials Research Center, Anhui University, Hefei 230601, Anhui, China
^bShanxi Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China

Received:2023-12-17 Accepted:2024-02-14 Online:2024-04-18 Published:2024-04-15
Contact: *E-mail: wangjz@ahu.edu.cn (J. Wang), wangjy@sxicc.ac.cn (J. Wang).
Supported by:
The National Natural Science Foundation of China(22279001);The National Natural Science Foundation of China(22179138);The Natural Science Foundation of Shanxi(20210302123005);The Anhui Science and Technology Major Project(2022e03020007)

摘要/Abstract

摘要：

催化氧反应(ORR)是锌空电池和氢燃料电池能量转化的关键过程, 然而其反应速率往往较低, 因此开发高活性且耐久的催化材料至关重要. 当前, 研发低成本、高效率且稳定的氧还原催化剂已成为国内外的研究热点. 其中, 富含金属-氮-碳活性位点的低成本ORR催化材料, 因其具有替代贵金属的潜力, 成为重要的候选材料. 然而, 在制备这类催化剂时, 所用分子前驱体在热解过程中易团聚形成金属基硬颗粒, 如何减少热解过程中金属成分的自发聚集和不良副产物的生成, 提高活性单原子的利用率, 特别是在使用廉价分子前驱体（如三聚氰胺和铁盐）时, 仍面临挑战. 本研究旨在探索有效的制备策略, 以优化催化剂性能, 推动其在能源转换领域的应用.

本文报道了一种以硝酸铋为牺牲剂, 石墨烯为导电载体, 通过热解廉价的三聚氰胺和铁盐, 合成石墨烯负载丰富Fe-N-C活性位点催化剂的新方法. 该方法中硝酸铋前驱体高温热解生成的铋铁合金或氧化铋因表面没有碳层, 而容易被热酸除去, 形成更多的可接近的FeNx活性位点, 从而有效地抑制铁基颗粒和管状碳结构的形成, 实现了催化剂的高效合成. 双球差矫正电镜、X-射线光电子能谱和X-射线吸收结构光谱等表征证明, 铋化合物去除后留下空位被铁原子取代, 增加了Fe-N-C位点密度, 并且铁以单原子活性位形式存在. 实验结果表明, 所制备的催化剂表现出高氧还原性能, 在碱性和酸性条件下的半波电位分别为0.916和0.784 V. 石墨烯基催化剂的动力学电流密度(0.9 V vs. RHE)达到10.41 mA cm^-2, 是不加铋化合物样品的6倍, 贵金属Pt/C催化剂的4倍. 此外, 催化剂的塔菲尔斜率为59 mV dec^-1, 低于不加铋化合物样品(80 mV dec^-1)、不加石墨烯样品(93 mV dec^-1)、无金属样品(88 mV dec^-1)和Pt/C (80 mV dec^-1). 在0.1 mol L^-1 KOH条件下, 催化剂循环10000圈后, 半波电位仅衰减15 mV, 低于Pt/C (36 mV)和无铋对照样 (20 mV), 表明催化剂具有较好的稳定性. 由于电化学法制备的石墨烯比热解法制备的非晶碳具有更好的耐腐蚀性, 从而可以提高阴极氧还原的稳定性. 另外, 所制备的催化剂应用在锌-空气电池中时, 最大功率密度可达201.4 mW cm^-2, 且循环1000次后电池电压几乎没有衰减.

综上, 本研究通过引入铋化合物, 显著提升了廉价前驱物铁-三聚氰胺的金属单原子化效率. 利用电化学法合成了石墨烯负载的Fe-N-C催化活性位, 制备出高活性、高稳定的催化剂. 将该低成本催化剂应用于锌-空气电池的阴极, 其表现出良好的长循环性能. 本研究为制备低成本、高性能的金属-氮-碳基电催化剂提供了新思路.

关键词: 氧还原反应, 铋, 石墨烯, 锌-空气电池, Fe-N-C

Abstract:

Synthesizing low-cost electrocatalysts with rich metal-nitrogen-carbon active sites for the oxygen reduction reaction (ORR) is critical for developing high-performance Zn-air batteries. However, it is challenging for the pyrolysis cheap molecular precursors (such as melamine and iron salts) is challenging because of the spontaneous aggregation of metal components and undesired byproducts during pyrolysis. Herein, we describe an approach to generate graphene-supported accessible Fe-N-C active sites by introducing a removable bismuth compound that efficiently inhibits the formation of iron-related particles and tubular carbon structures. The graphene-supported Fe(Bi)-N-C electrocatalyst exhibited high ORR activity under both alkaline (E_1/2 ~0.916 V) and acidic (E_1/2 ~0.784 V) conditions, along with excellent durability (15 mV degradation after 10 k cycles accelerated test). Using the catalytic material as the cathode, the Zn-air battery delivered a high power density of 201.4 mW cm^-2 and a high stability over 1000 cycles. This investigation presents a promising controlled pyrolysis solution for the scalable synthesis of low-cost, high-performance metal-nitrogen-carbon-based catalytic materials.

Key words: Oxygen reduction reaction, Bismuth, Graphene, Zn-air battery, Fe-N-C

杨志远, 张燕, 肖娟定, 王俊英, 王俊中. 铋牺牲法制备石墨烯负载Fe-N单原子位点增效氧还原催化和锌-空气电池性能[J]. 催化学报, 2024, 59: 272-281.

Zhiyuan Yang, Yan Zhang, Juanding Xiao, Junying Wang, Junzhong Wang. Enhancing oxygen reduction of Fe-N-C active sites onto graphene via bismuth sacrifice for Zn-air batteries[J]. Chinese Journal of Catalysis, 2024, 59: 272-281.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60002-1

https://www.cjcatal.com/CN/Y2024/V59/I4/272

图/表 7

Fig. 1. Schematic illustration of the synthesis of dense Fe-N-C sites anchored onto graphene.

Fig. 2. Material synthesis and structure characterization. XRD patterns (a,b) and Raman spectra (c) of the catalysts. (d) Isothermal N2 adsorption-desorption plots of Fe(Bi)-N-C/G-A, Fe-N-C/G-A, and (Bi)-N-C/G-A.

Fig. 3. Morphology characterization of Fe(Bi)-N-C/G-A. (a) SEM image. (b) TEM image. (c,d) EDS elemental mappings. (e) HAADF-STEM micrographs of Fe(Bi)-N-C/G-A. (f) EELS of the framed area in (e).

Fig. 4. (a) XPS survey spectrum of Fe(Bi)-N-C/G-A, Fe-N-C/G-A, (Bi)-N-C/G-A, and N-C/G-A. (b,c) High-resolution Fe 2p and N 1s XPS spectra of Fe(Bi)-N-C/G-A and Fe-N-C/G-A. (d) N species in Fe(Bi)-N-C/G-A and Fe-N-C/G-A.

Fig. 5. Atomic structural analysis of as-prepared samples. (a) Fe K-edge XANES spectra. (b) FT k2-weighted Fe K-edge EXAFS spectra. (c,d) EXAFS fitting results in R space. (e) Fe K-edge wavelet transform of EXAFS for Fe(Bi)-N-C/G-A, with Fe-N-C/G-A, FePc, and Fe foil used as references.

Fig. 6. Electrochemical ORR activity of as-prepared samples. LSV curves (a) and Jk (at 0.9 V) and E1/2 (b). (c) Corresponding Tafel profile. (d) Polarization curves for Fe(Bi)-N-C/G-A at different rotation speeds (inset: K-L plot for Fe(Bi)-N-C/G-A). (e) Electron transfer numbers and H2O2 yield of Fe(Bi)-N-C/G-A, Fe-N-C/G-A, (Bi)-N-C/G-A, N-C/G-A, and Pt/C in 0.1 mol L-1 KOH solution. (f) Stability measurement of Fe(Bi)-N-C/G-A, Fe-N-C/G-A and Pt/C in O2-saturated 0.1 mol L-1 KOH solution. (g) Double-layer capacitor (Cdl) of Fe(Bi)-N-C/G-A and Fe-N-C/G-A. (h) LSV curves of Fe(Bi)-N-C/G-A, Fe-N-C/G-A, (Bi)-N-C/G-A, N-C/G-A, and commercial Pt/C at a sweep rate of 5 mV s-1 in O2-saturated 0.1 mol L-1 HClO4 solution.

Fig. 7. Zn-air battery performance. Open-circuit potential curves (a), discharge polarization and the corresponding power density curves (b) of Zn-air batteries with Fe(Bi)-N-C/G-A, Fe-N-C/G-A, and Pt/C as air cathodes. (c) Specific capacity plot at 20 mA cm-2. (d) Galvanostatic charging/discharging cycling curves of Fe(Bi)-N-C/G-A + RuO2 and Pt/C + RuO2 air cathodes at 5 mA cm-2.

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铋牺牲法制备石墨烯负载Fe-N单原子位点增效氧还原催化和锌-空气电池性能

Enhancing oxygen reduction of Fe-N-C active sites onto graphene via bismuth sacrifice for Zn-air batteries

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