Research Progress of in Situ Exsolution of Electrode Surface of Solid Oxide Fuel Cells

doi:10.19894/j.issn.1000-0518.230141

Chinese Journal of Applied Chemistry ›› 2023, Vol. 40 ›› Issue (10): 1335-1346.DOI: 10.19894/j.issn.1000-0518.230141

• Review •

Research Progress of in Situ Exsolution of Electrode Surface of Solid Oxide Fuel Cells

Jun-Ling MENG¹, Chuan TIAN¹^,², Na XU¹, Li-Na ZHAO¹, Hai-Xia ZHONG²(), Zhan-Lin XU¹()

^1.Key Laboratory of Preparation and Applications of Environmental Friendly Materials，Ministry of Education，College of Chemistry，Jilin Normal University，Siping 136000，China
^2.State Key Laboratory of Rare Earth Resource Utilization，Changchun Institute of Applied Chemistry，Chinese Academy of Sciences，Changchun 130022，China

Received:2023-05-12 Accepted:2023-08-18 Published:2023-10-01 Online:2023-10-13
Contact: Hai-Xia ZHONG,Zhan-Lin XU
About author:xuzhanlin1964@163.com
hxzhong@ciac.ac.cn
Supported by:
the National Natural Science Foundation of China(52002369);the Scientific and Technological Developing Project of Jilin Province(20220101097JC);the Research Program on Science and Technology from the Education Department of Jilin Province(JJKH20230495KJ);the Open Funds of the State Key Laboratory of Rare Earth Resource Utilization(RERU2022009);the Key Laboratory for Comprehensive Energy Saving of Cold Regions Architecture of Ministry of Education, Jilin Jianzhu University(JLJZHDK202205)

Abstract

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

CLC Number:

O643

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.

Figures/Tables 5

Fig.1 Schematic diagram of typical structure of perovskite oxides

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

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

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］

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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Research Progress of in Situ Exsolution of Electrode Surface of Solid Oxide Fuel Cells

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