一体式可再生燃料电池双功能氧催化剂的研究进展

doi:10.13208/j.electrochem.2205301

电化学（中英文） ›› 2023, Vol. 29 ›› Issue (7): 2205301. doi: 10.13208/j.electrochem.2205301

所属专题： “电催化和燃料电池”专题文章

一体式可再生燃料电池双功能氧催化剂的研究进展

郑天龙^a, 欧明玉^b, 徐松^a, 毛信表^b^,^*(), 王释一^a, 和庆钢^a^,^*()

^a浙江大学化学工程与生物工程学院，浙江杭州 310027
^b浙江工业大学化学工程学院，浙江杭州 310014

收稿日期:2022-05-30 修回日期:2022-06-29 接受日期:2022-07-14 出版日期:2023-07-28 发布日期:2022-07-20
通讯作者: * Tel:（86-571）88813899, E-mail: xbmao@zjut.edu.cn;Tel:（86-571）87701916, E-mail: qghe@zju.edu.cn
作者简介:^#郑天龙、欧明玉、徐松对于此工作具有同等贡献
基金资助:
国家自然科学基金(21978260);国家自然科学基金(22178307)

Recent Progress of Bifunctional Electrocatalysts for Oxygen Electrodes in Unitized Regenerative Fuel Cells

Tian-Long Zheng^a, Ming-Yu Ou^b, Song Xu^a, Xin-Biao Mao^b^,^*(), Shi-Yi Wang^a, Qing-Gang He^a^,^*()

^aCollege of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China
^bCollege of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China

Received:2022-05-30 Revised:2022-06-29 Accepted:2022-07-14 Published:2023-07-28 Online:2022-07-20

摘要/Abstract

摘要：

双功能氧催化剂的催化活性及稳定性是决定一体式可再生燃料电池能否高效运作的关键因素之一。得益于分别对于氧还原及氧析出反应特定中间产物适当的结合能，铂与铱、钌及其氧化物所制成的贵金属催化剂，常被应用于一体式可再生燃料电池中作为双功能氧催化剂。同时，近年来对于非铂族双功能氧催化剂的研究也取得了较大进展。本篇综述从一体式可再生燃料电池中氧还原及氧析出反应的作用机理出发，首先着重对传统铂基双功能催化剂的构效关系进行了总结，其次介绍了钙钛矿型、尖晶石型氧化物、非金属等新型双功能氧催化剂的发展趋势。此外，本文对于该研究领域所存在的限制条件和发展路线也进行了总结与展望。

关键词: 一体式可再生燃料电池, 双功能氧催化剂, 氧还原反应, 氧析出反应, Pt基电催化剂, 非Pt族电催化剂

Abstract:

Unitized regenerative fuel cells (URFCs), which oxidize hydrogen to water to generate electrical power under the fuel cells (FCs) mode and electrolyze water to hydrogen under the water electrolysis (WE) mode for recycling, are known as clean and sustainable energy conversion devices. In contrast to the hydrogen oxidation reaction (HOR) and hydrogen evolution reaction (HER) on the hydrogen electrode side, the sluggish kinetics of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) on the oxygen electrode side requires highly efficient bifunctional oxygen catalysts. Conventional precious metal catalysts combine Pt and IrO₂ with excellent ORR and OER activities to achieve bifunctional electrocatalysis performance, but the scarcity and high cost of precious metals have restricted their applications. Although platinum group metal (PGM)-free bifunctional catalysts circumvent the problems of high price and scarce resources, they suffer from insufficient activity and poor stability. Therefore, much attention has been paid by researchers on developing efficient, durable and low-cost bifunctional oxygen catalysts. In this review, we mainly introduce the recent advances in bifunctional oxygen catalysts for URFCs focusing on the catalyst design, activity, and durability. First of all, the fundamental understanding of the ORR and OER mechanisms is essential prior to discussing the development of bifunctional oxygen catalysts. Starting from activity descriptor-based approaches in the identification of catalyst activity, this review summarizes the alternative catalyst design strategies confronted with the unfavorable scaling relationship existing among the binding energies of different oxygen-containing reaction intermediates during ORR and OER. Subsequently, in addition to introducing the design strategies of conventional PGM-based bifunctional catalysts, the recent progress of PGM-free bifunctional catalysts, including perovskite oxides, spinel oxides, other transition metal compounds, and carbon-based (non-metal) catalysts, is presented in terms of their structure-property relationship. Various strategies have been developed by researchers to optimize the performance of PGM-free bifunctional catalysts, such as nanostructuring, defects engineering, heteroatom doping, phase and composition modulation, support coupling and morphology engineering, etc. Some PGM-free bifunctional catalysts reported in the literature show promising ORR and OER activities superior to Pt+IrO₂ in an alkaline environment. In general, although great progress has been made on PGM-free bifunctional electrocatalysts, their cycling durability is still far from that of precious metal catalysts, and few of them have been applied in acidic environments. Therefore, much more efforts are needed to improve the stability of PGM-free bifunctional catalysts. Lastly, the challenge and future development of designing optimal bifunctional oxygen catalysts are discussed.

Key words: Unitized regenerative fuel cell, Bifunctional electrocatalyst, Oxygen reduction reaction, Oxygen evolution reaction, Pt-based electrocatalyst, Non-Pt group electrocatalyst

郑天龙, 欧明玉, 徐松, 毛信表, 王释一, 和庆钢. 一体式可再生燃料电池双功能氧催化剂的研究进展[J]. 电化学（中英文）, 2023, 29(7): 2205301.

Tian-Long Zheng, Ming-Yu Ou, Song Xu, Xin-Biao Mao, Shi-Yi Wang, Qing-Gang He. Recent Progress of Bifunctional Electrocatalysts for Oxygen Electrodes in Unitized Regenerative Fuel Cells[J]. Journal of Electrochemistry, 2023, 29(7): 2205301.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.2205301

https://electrochem.xmu.edu.cn/CN/Y2023/V29/I7/2205301

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Electrocatalyst	Preparation method	Performance	Structure feature	Ref
Pt/Ir₃(IrO₂)₇	Microwave-assisted polyol process	ORR (21.71 mA·mg^-1 at 0.85 V), OER（42.35 mA·mg^-1 at 1.55 V）	The introduction of Ir into IrO₂ support improves electronic conductivity and the overall performance	[21]
Ir@Pt nanodendrites	Impregnation-reduction method	Higher ORR/OER activity than the mixture of Ir and Pt blacks	Good dispersion of Pt, interaction between Pt and Ir, and special morphology of Ir@Pt nanodendrites	[22]
Pt/porous-IrO₂	Microwave-assisted polyol process	ORR: 2.3 times that of Pt/com-IrO₂, OER: 28% higher than Pt/com-IrO₂	The porous IrO₂provides internal and external sites for Pt deposition	[23]
Pt@Ir black	Galvanic replacement	ORR: mass activity of 373.3 mA·mg_Pt^-1 (2.6 times that of Pt black), OER: comparable performance with Ir black	Good dispersion of Pt nanodots on Ir black and the synergistic effect between the Pt and underlying Ir atoms	[24]
Ir@Pt-nanorods	Polyol method	ORR stability>Pt nanorods, OER stability <Ir	Good dispersion of Ir nanodots on Pt nanorods	[25]
PtIr/Ti₄O₇	Impregnation-reduction method	Higher ORR and OER performance than Pt/C and Pt/Ti₄O₇	Formation of PtIr alloy phase, highly stable Ti₄O₇ support in an acid medium, and interaction between catalyst and support	[26]

Electrocatalyst	Preparation method	Performance	Structure features	Ref.
meso-Co₃O₄	Hard template method	η_ORR =623 mV (-3 mA·cm^-2) and η_OER=411 mV (10 mA·cm^-2)	High surface area and gyroid network structure in the ordered mesoporous Co₃O₄	[48]
Co₃O₄ nanochains	Cobalt oxalate pyrolysis	ORR: E_1/2=0.84 V (<Pt/C 20 mV), η_OER=320 mV (0.5 mA·cm^-2); higher ORR stability than Pt/C	Surface octahedral Co³⁺ site for OER, Co²⁺ (tetrahedral sites) for ORR	[49]
NiCo₂O₄ ultrathin nanosheets	Coprecipitation method	ORR: E_onset=0.85 V OER: η_onset=340 mV; ΔE, increase of 0.14 V (after 29 h durability test)	The oxygen vacancies promote the reactivity of active sites, and the ultrathin structure increases the number of active sites	[50]
Dual-Phase MnCo₂O₄/ CNTs	Hydrothermal method	Comparable ORR activity, superior OER activity and higher stability with regard to Pt/C	Synergic covalent coupling between nanocarbons and MnCo₂O₄ facilitating charge transfer	[51]
3D hierarchical porous CoFe₂O₄, hollow nanospheres	Hydrothermal method	ORR: E_1/2(CoFe2O4)<E_1/2(Pt/C) ca. 180 mV, η_OER=440 mV (10 mA·cm^-2); higher ORR/OER stability than Pt/C	3D hierarchical porous structure	[52]

Electrocatalyst	Preparation method	Performance	Structure feature	Ref.
P-doped carbon nanosheets (2D-PPCN）	Multifunctional template method	Comparable ORR and OER activities to those of Pt/C and Ir/C, respectively; superior durability to that of Pt/C+Ir/C	20-35-nm-thick 2D morphology, P-doping, and porosity tunability	[72]
P,N Co-doped graphene frameworks (PNGF)	One-pot hydrothermal method	ΔE=705 mV (Pt/C+Ir/C:769 mV); almost zero change in overpotential after 5000 cycles	Intensifying the P-N sites for OER and N-doped sites for ORR	[75]
Defect-enriched and pyridinic-N dominated graphene nanosheets (DN-CP@G)	In situ exfoliating graphene from carbon paper and PN dopants	Comparable ORR and OER activities to those of Pt/C and Ir/C, respectively; superior durability to that of Pt/C+Ir/C	Abundant defective sites and active PN dopants, interconnected graphitic carbon fiber core	[77]
3D P,S co-doped carbon nitride sponges (P,S-CNS)	Polymerization and pyrolysis of aminoguanidine	ORR: E_onset=0.97 V, superior to Pt/C, OER: E=1.56 V (10 mA·cm^-2), comparable to RuO₂; good ORR/OER stability within 210 h	3D P,S co-doped carbon nitride and efficient mass/charge transfer	[78]
Carbon fiber@porous carbon cloth (o-CC-H₂)	High-temperature H₂ etching method	OER: E= 1.618 V (10 mA·cm^-2), ORR peak potential is 0.565 V; good ORR/OER stability after 900 cycles (9 h)	Carbon fibers coated by defects enriched porous graphene nanosheet skin.	[79]

一体式可再生燃料电池双功能氧催化剂的研究进展

Recent Progress of Bifunctional Electrocatalysts for Oxygen Electrodes in Unitized Regenerative Fuel Cells

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