固体氧化物燃料电池电极表面原位析出的研究进展

doi:10.19894/j.issn.1000-0518.230141

摘要/Abstract

摘要：

固体氧化物燃料电池（Solid oxide fuel cells， SOFC）是一种能量转换装置，具有转换效率高、环境友好和燃料适应性强等优点，其中，电极作为电化学反应场所，对SOFC的性能起关键作用。相较于传统的SOFC电极，表面析出纳米颗粒后电极表现出较强的催化活性和优异的电化学性能。本文就钙钛矿型电极材料表面原位析出的研究予以总结。首先，探讨钙钛矿的晶体结构类型对电极表面原位析出的影响；其次，详细地介绍了钙钛矿中各种缺陷对析出纳米颗粒的影响；而后对比了目前主要的两种原位析出方式，并对不同的析出产物进行了分析。最后，提出了目前SOFC电极表面原位析出研究所面临的难点与挑战，并对其未来的发展方向进行了总结，这为以后相关的研究指明了方向。

关键词: 固体氧化物燃料电池, 钙钛矿, 电极材料, 原位析出, 电化学性能

Abstract:

Solid oxide fuel cells （SOFCs） are energy conversion devices with high conversion efficiency， environmental friendliness， and wide fuel adaptability. As the place of electrochemical reactions， electrodes play a key role in the performance of SOFCs. Compared with the conventional electrode materials， the electrode with nanoparticles exsolved on the surface show stronger catalytic activity and excellent electrochemical performance. In this article， the investigations of in situ exsolution of perovskite-type electrode materials are summarized. Firstly， the effect of the crystal structure of perovskite on exsolution of electrode is discussed. Secondly， the influences of defects in perovskite on the exsolution of nanoparticles are introduced in detail. And then two main methods for in situ exsolution are compared and different exsolved products are analyzed. Finally， the difficulties and challenges faced to the in situ exsolution investigation for the SOFC electrode are put forward on the basis of the existing research， which points out the direction for future study.

Key words: Solid oxide fuel cells, Perovskite, Electrode materials, In situ exsolution, Electrochemical performance

中图分类号:

O643

孟君玲, 田川, 徐娜, 赵丽娜, 钟海霞, 徐占林. 固体氧化物燃料电池电极表面原位析出的研究进展[J]. 应用化学, 2023, 40(10): 1335-1346.

Jun-Ling MENG, Chuan TIAN, Na XU, Li-Na ZHAO, Hai-Xia ZHONG, Zhan-Lin XU. Research Progress of in Situ Exsolution of Electrode Surface of Solid Oxide Fuel Cells[J]. Chinese Journal of Applied Chemistry, 2023, 40(10): 1335-1346.

图/表 5

图1 钙钛矿氧化物的常见结构类型示意图

Fig.1 Schematic diagram of typical structure of perovskite oxides

图2 在氢气气氛900 ℃下化合物中金属阳离子被还原为金属的吉布斯自由能曲线［31-35］

Fig.2 Gibbs free energy of reduction of oxides to either metals at 900 ℃ in H2［31-35］

表1 不同结构类型的钙钛矿电极材料原位析出的研究以及代表性材料

Table 1 Study on exsolution of SOFC electrode with different structure types of perovskite and representative materials

Structure types	Representative materials	Exsolved nanoparticles
Single perovskite	La_0.3Ca_0.7Fe_0.7Cr_0.3O_3?_δ^［43］	Ni-Fe alloy
	Pr_0.4Sr_0.6Co_0.2Fe_0.7Nb_0.1O_3?_δ^［44］	Co₃Fe₇ alloy
	La_0.5Sr_0.5Fe_0.9Mo_0.1?_x Ni _x O_3?_δ^［45］	Fe-Ni alloy
	Ni-La_0.8Sr_0.2FeO_3?_δ^［46］	Ni-Fe alloy
	SrFe_0.85Ti_0.1Ni_0.05O_3?_δ^［47］	NiO
Double perovskite	（PrBa）_0.95Fe_2?_x Ti _x O_6?_δ^［48］	Fe
	SrBiFeTiO_6?_δ^［49］	Bi and Fe
	Sr_1.95Fe_1.4Co_0.1Mo_0.5O_6?_δ^［50］	Co
	Sr₂FeMo_1?_x Co _x O_6?_δ^［51］	Co-Fe alloy
	La_0.5Sr_1.5Fe_1.5Mo_0.5O_6?_δ^［52］	Fe
Ruddlesden-Popper perovskite	（La_0.6Sr_1.4）_0.95Mn_0.9B_0.1O₄ （B=Co，Ni，Cu）^［53］	Co， Ni， Cu
	（LaSr）_0.9Fe_0.9Cu_0.1O₄^［54］	Cu
	La_1.5Sr_1.5Mn_1.5Ni_0.5O₇^［55］	Ni
	（Pr_0.4Sr_0.6）₃（Fe_0.85Nb_0.15）₂O₇^［56］	Co-Fe alloy
	La_1.2Sr_0.8Mn_0.4Fe_0.6O₄^［57］	Fe
A-site-deficient perovskite	La_0.4Sr_0.4Ti_0.94Ni_0.06O_3?_δ^［58］	Ni
	Pr_0.4Sr_0.5Co _x Fe_0.9?_x Mo_0.1O_3?_δ^［59］	Co-Fe alloy
	（Ba_0.2Sr_0.8）_0.9Ni_0.07Fe_0.63Mo_0.3O_3?_δ^［60］	NiFe/NiFeO _x core-shell structure
	（Pr_0.5Sr_0.5）_0.9Fe_0.8Ru_0.1Nb_0.1O_3?_δ^［61］	FeRu/FeO _x core-shell structure
	La_0.6Sr_0.2Cr_0.85Ni_0.15O₃^［62］	Ni

图3 钙钛矿的非化学计量比对原位析出的关键作用示意图。（A）金属颗粒从样品中原位析出的示意图；（B）具有A位缺陷的钙钛矿氧化物的表面析出方程式（方程1）和无阳离子缺陷的钙钛矿氧化物的表面析出方程式（方程2）；（C）钙钛矿氧化物非化学计量比的笛卡尔坐标图［27］

Fig.3 Schematic diagram of the key role of in situ exsolution in non-stoichiometric perovskite. （A） Schematic diagram of the in situ exsolution of metal particles from the sample；（B） Equation of exsolution from perovskite oxides with A-site defects （equation 1） and without cationic defects （equation 2）；（C） Cartesian plot of the non-stoichiometric perovskite oxides. Compared to perfect ABO3， non-stoichiometric perovskites with excess ions in the lattice are located in the first quadrant and non-stoichiometric perovskites with defects in the lattice are located in the third quadrant［27］

图4 氢气还原和电还原原位析出方式的对比。（A）原位析出过程示意图；（B）通过氢气还原的方式析出金属纳米颗粒的电池示意图；（C）通过电还原的方式析出金属纳米颗粒电池示意图；（D）蓝色曲线为热重数据，显示氢气还原后氧损失随时间的变化，橙色曲线为外加2 V电压后，电流密度随时间的变化；（E）在900 ℃氢气还原20 h后的形貌图；（F）图E的形貌放大图；（G）在900 ℃电还原150 s后的形貌图；（H）图G的形貌放大图；（I）电还原后的电池在750 ℃运行100 h后的形貌图；（J）图I的形貌放大图；（K）平行坐标系中E-J的样品的各种特性曲线［28］

Fig.4 Comparison of the in situ exsolution methods by hydrogen reduction and electric reduction. （A） Schematic diagram of the in situ exsolution process；（B） Metal nanoparticles are exsoluted by hydrogen reduction；（C） Metal nanoparticles are exsoluted by electric reduction；（D） The blue curve is the TG data， showing the change of oxygen loss with time after hydrogen reduction， and the orange curve is the change of current density with time after the application of 2 V voltage. SEM micrographs of electrodes surface；（E） Reduction by hydrogen at 900 ℃ for 20 h；（F） The enlarged morphology of figure E；（G） Electrochemical switching under 900 ℃ for 150 s；（H） The enlarged morphology of figure G；（I） Fuel cell testing at 750 ℃ for 100 h after electrochemical reduction；（J） The enlarged morphology of figure I；（K） Various characteristics of the samples shown in E-J， plotted in a parallel coordinate system［28］

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