富含吡啶氮-钴活性位点的三维多级大/介孔石墨烯作为高效可逆氧电催化剂用于可充电锌-空气电池

doi:10.1016/S1872-2067(20)63642-7

催化学报 ›› 2021, Vol. 42 ›› Issue (4): 571-582.DOI: 10.1016/S1872-2067(20)63642-7

富含吡啶氮-钴活性位点的三维多级大/介孔石墨烯作为高效可逆氧电催化剂用于可充电锌-空气电池

周省, 覃佳艺, 赵雪茹, 杨静^*()

天津大学材料科学与工程学院新能源材料研究所, 先进陶瓷与加工技术教育部重点实验室, 天津300072

收稿日期:2020-04-27 接受日期:2020-05-31 出版日期:2021-04-18 发布日期:2021-01-22
通讯作者: 杨静
基金资助:
国家自然科学基金(51572188);国家自然科学基金(51822106)

3D hierarchically macro-/mesoporous graphene frameworks enriched with pyridinic-nitrogen-cobalt active sites as efficient reversible oxygen electrocatalysts for rechargeable zinc-air batteries

Sheng Zhou, Jiayi Qin, Xueru Zhao, Jing Yang^*()

Institute of New-Energy Materials, Key Laboratory of Advanced Ceramics and Machining Technology of Ministry of Education, School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China

Received:2020-04-27 Accepted:2020-05-31 Online:2021-04-18 Published:2021-01-22
Contact: Jing Yang
About author:^*Tel: +86-22-85356663; E-mail: yang_jing@tju.edu.cn
Supported by:
National Natural Science Foundation of China(51572188);National Natural Science Foundation of China(51822106)

摘要/Abstract

摘要：

随着能源危机的日益严峻, 能源的储存和转换越来越受到人们的重视. 目前人们加以开发和利用的清洁能源主要包括太阳能、风能、氢能、地热能以及电化学能等. 其中, 燃料电池和金属-空气电池等作为电化学器件为电化学能的开发及可持续利用提供了条件. 特别是金属-空气电池以电极电位较负的金属如镁、铝、锌、铁等作负极, 以空气中的氧或纯氧作正极, 具有比能量高、性能稳定、价格便宜的特点. 氧还原反应(ORR)和析氧反应(OER)是可再生电化学能量转换和储存过程中的两个关键电化学过程. 贵金属(Pt/C, Ir/C, IrO₂等)虽然具有高催化活性, 但价格昂贵、资源匮乏限制了其大规模的使用和发展. 此外, 它们的催化性能单一, 难以同时实现多反应的高效催化. 目前, 大量研究工作集中在开发低成本、高效的ORR和OER催化剂, 用来代替昂贵的铂类贵金属催化剂. 在能源器件设计中, 由于OER和ORR反应发生在同一个电极上, 若能制备出具有ORR和OER双功能催化性能的电催化剂, 将在很大程度上降低能源器件的设计难度. 最近, 我们的研究工作揭示了吡啶-氮-钴(pyri-N-Co)配位结构在协同作用中的重要性, 协同作用大幅度提升了NiCo₂O₄/N掺杂石墨烯的本征催化活性. 虽然金属粒子与掺氮石墨烯的结合有利于催化活性和稳定性的提高, 但二维石墨烯片之间由于π-π键相互作用, 容易聚集和堆叠. 在实际应用中, 石墨烯片之间的堆叠会导致可达表面的损失, 从而使复合催化剂利用率降低, 结构稳定性变差. 因此, 制备富含充分暴露且高效的ORR/OER活性中心的电催化剂仍然是一个巨大挑战.
本文采用激光辐照法和水热法制备了具有层间大孔和片内介孔相互交联结构且负载铁酸钴纳米颗粒的三维多级孔石墨烯复合电催化剂(CoFe/3D-NLG), 研究了其微观结构与ORR/OER电催化性能的关系. 比表面积和X射线光电子能谱测试结果表明, CoFe/3D-NLG具有大的比表面积(322.6 m² g^-1)和孔体积(0.715 cm³ g^-1), 并且富含吡啶氮-钴活性中心. 电化学测试表明, 对于OER电催化, CoFe/3D-NLG复合催化剂在10 mA cm^-2处的过电势为304 mV, 优于商用RuO₂催化剂的322 mV; 对于ORR电催化, CoFe/3D-NLG的半波电位达到872 mV, 非常接近商用Pt/C催化剂(876 mV). 此外, 作为可充电锌空气电池的空气电极催化剂, CoFe/3D-NLG展现出了超高的开路电压(1.56 V)、高功率密度(213 mW cm^-2)以及超低充放电电压(0.63 V), 并且具有良好的充放电循环稳定性. CoFe/3D-NLG优异的ORR/OER电催化性能主要归因于以下两点: 1)大量的吡啶氮-钴活性位点极大地加快了缓慢的氧电催化动力学, 提高了每个活性位点的ORR/OER本征催化活性; 2)丰富的层间大孔和面内介孔多级孔结构促进了整个石墨烯结构中的高效传质, 因而在电催化过程中吡啶氮-钴活性位点得以充分暴露于电解液中.

关键词: 多级孔, 复合催化剂, 氧电催化, 尖晶石氧化物, 可充电锌-空气电池

Abstract:

Efficient and affordable electrocatalysts for reversible oxygen reduction and oxygen evolution reactions (ORR and OER, respectively) are highly sought-after for use in rechargeable metal-air batteries. However, the construction of high-performance electrocatalysts that possess both largely accessible active sites and superior ORR/OER intrinsic activities is challenging. Herein, we report the design and successful preparation of a 3D hierarchically porous graphene framework with interconnected interlayer macropores and in-plane mesopores, enriched with pyridinic-nitrogen-cobalt (pyri-N-Co) active sites, namely, CoFe/3D-NLG. The pyri-N-Co bonding significantly accelerates sluggish oxygen electrocatalysis kinetics, in turn substantially improving the intrinsic ORR/OER activities per active site, while copious interlayer macropores and in-plane mesopores enable ultra-efficient mass transfer throughout the graphene architecture, thus ensuring sufficient exposure of accessible pyri-N-Co active sites to the reagents. Such a robust catalyst structure endows CoFe/3D-NLG with a remarkably enhanced reversible oxygen electrocatalysis performance, with the ORR half-wave potential identical to that of the benchmark Pt/C catalyst, and OER activity far surpassing that of the noble-metal-based RuO₂ catalyst. Moreover, when employed as an air electrode for a rechargeable Zn-air battery, CoFe/3D-NLG manifests an exceedingly high open-circuit voltage (1.56 V), high peak power density (213 mW cm^-2), ultra-low charge/discharge voltage (0.63 V), and excellent charge/discharge cycling stability, outperforming state-of-the-art noble-metal electrocatalysts.

Key words: Hierarchical pores, Composite catalyst, Oxygen electrocatalysis, Spinel oxide, Rechargeable zinc-air battery

周省, 覃佳艺, 赵雪茹, 杨静. 富含吡啶氮-钴活性位点的三维多级大/介孔石墨烯作为高效可逆氧电催化剂用于可充电锌-空气电池[J]. 催化学报, 2021, 42(4): 571-582.

Sheng Zhou, Jiayi Qin, Xueru Zhao, Jing Yang. 3D hierarchically macro-/mesoporous graphene frameworks enriched with pyridinic-nitrogen-cobalt active sites as efficient reversible oxygen electrocatalysts for rechargeable zinc-air batteries[J]. Chinese Journal of Catalysis, 2021, 42(4): 571-582.

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Fig. 1. (a) Synthetic scheme for the CoFe/3D-NLG catalyst. (b) SEM image of 3D-NLG. (c) TEM image of CoFe/3D-NLG. The inset shows the corresponding SAED pattern. (d) HR-TEM image of the NPs and (e) TEM image of the in-plane mesopores on the graphene sheet of CoFe/3D-NLG, as indicated by the yellow circles in c. (f) Pore size distribution, (g) N2 adsorption-desorption isotherm curves, and (h) Raman spectra of CoFe/NG, CoFe/NLG, CoFe/3D-NG, and CoFe/3D-NLG.

Fig. 2. (a) N K-edge EELS profiles of CoFe/NG and CoFe/3D-NLG. (b) N 1s XPS profiles of CoFe/3D-NLG, CoFe/NG, and 3D-NLG. (c) Co 2p XPS profiles, (d) Co L-edge EELS profiles, and (e) Raman spectra of CoFe, CoFe/NG, and CoFe/3D-NLG. (f) Raman spectra of NG, 3D-NLG, and CoFe/3D-NLG.

Fig. 3. (a) OER LSV curves, (b) Tafel plots, and (c) Nyquist plots of CoFe/NG, CoFe/NLG, CoFe/3D-NG, CoFe/3D-NLG, and RuO2. The inset in (c) shows the equivalent circuit used to calculate charge transfer resistance of the catalysts, where Rs is the electrolyte resistance, Rct is the charge transfer resistance, and Cdl represents the double-layer capacitance. (d) Charging current density plots with varying scan rates for the samples. (e) Comparison of the ECSA and OER specific activity of different samples. (f) Chronoamperometric response (i-t) curves of CoFe/3D-NLG and RuO2.

Fig. 4. (a) ORR LSV curves measured in O2-saturated 0.1 M KOH solution (rotation rate: 1600 rpm). (b) Corresponding bar plots of onset potential (Eonset) and half-wave potential (E1/2). (c) Tafel plots. (d) Comparison of the ORR mass activity at 0.7 V vs. RHE. (e) i-t curve before and after the addition of 1.0 M methanol. (f) Chronoamperometric response of CoFe/3D-NLG and Pt/C at 0.7 V vs. RHE. The inset shows the ORR LSV curves before and after 10 h of continuous polarization.

Fig. 5. (a) The overall polarization curves of CoFe/3D-NLG, CoFe/NG, and Pt/C + RuO2, measured in O2-saturated 1.0 M KOH solution. The inset shows the potential difference between ORR and OER (ΔE) for the catalysts. (b) Open-circuit plots, (c) galvanodynamic charge/discharge profiles and power density curves, (d) discharge curves at a constant current density of 10 mA cm-2, and (e) charge/discharge cycling curves at a current density of 5 mA cm-2 of Zinc-air batteries assembled with CoFe/3D-NLG and Pt/C + RuO2 (duration: 1200 s per cycle).

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富含吡啶氮-钴活性位点的三维多级大/介孔石墨烯作为高效可逆氧电催化剂用于可充电锌-空气电池

3D hierarchically macro-/mesoporous graphene frameworks enriched with pyridinic-nitrogen-cobalt active sites as efficient reversible oxygen electrocatalysts for rechargeable zinc-air batteries

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