Investigation on PrBaFe2O6-δ anode material with in-situ FeNi nanoparticle in direct carbon solid oxide fuel cell

doi:10.11949/0438-1157.20220264

Abstract

Abstract:

The development of high-performance anode materials is of great significance for the development of solid oxide fuel cells (SOFCs) fueled by solid carbon. In this paper, the application of PrBaFe₂O_6-_δ (PBF)-based layered double perovskite materials in SOFCs with in-situ precipitation of Fe and FeNi alloys was investigated. Ni-doped (PrBa)_0.95Fe_1.7Ti_0.2Ni_0.1O_6-_δ (PBFTN) anode material was prepared by sol-gel method. XRD showed that the as-synthesized material exhibited a perovskite structure and remained stable in an anodic reducing atmosphere. XRD, SEM, TEM, and XPS results showed that a large number of uniformly distributed nano-metal particles are precipitated on the surface of the material under reducing atmosphere, which is crucial for improving the output performance of the cell. When pure nano activated carbon was used as fuel, the electrolyte-supported single cell with PBFTN as anode achieved a maximum power density of 698 mW·cm^-2 at 800℃, which is excellent, indicating that it is a potential SOFCs anode material.

Key words: electrochemistry, fuel cells, in-situ precipitation, nanoparticles, anode materials, perovskites

摘要：

开发高性能阳极材料对于固体碳为燃料的固体氧化物燃料电池（solid oxide fuel cells， SOFCs）的发展意义重大。本文研究了原位析出Fe以及FeNi合金的PrBaFe₂O_6-_δ （PBF）基层状双钙钛矿材料在SOFCs中的应用。通过溶胶-凝胶法制备了Ni掺杂的 (PrBa)_0.95Fe_1.7Ti_0.2Ni_0.1O_6-_δ （PBFTN）阳极材料。XRD表明合成的材料呈现钙钛矿结构且在阳极还原性气氛下保持稳定。XRD、SEM、TEM、XPS结果表明在还原性气氛下材料表面析出大量均匀分布的纳米金属颗粒。当采用纯的纳米活性炭为燃料时，电解质支撑型的以PBFTN为阳极的单电池在800℃下实现了698 mW·cm^-2的最大功率密度，性能十分优异，表明其是一种具有潜力的SOFCs阳极材料。

关键词: 电化学, 燃料电池, 原位析出, 纳米颗粒, 阳极材料, 钙钛矿

CLC Number:

TQ 152

Chengyi AI, Jinshuo QIAO, Zhenhuan WANG, Wang SUN, Kening SUN. Investigation on PrBaFe₂O_6-_δ anode material with in-situ FeNi nanoparticle in direct carbon solid oxide fuel cell[J]. CIESC Journal, 2022, 73(8): 3708-3719.

艾承燚, 乔金硕, 王振华, 孙旺, 孙克宁. 原位析出纳米合金的PrBaFe₂O_6-_δ 基阳极构筑及其在固体碳燃料电池中的应用研究[J]. 化工学报, 2022, 73(8): 3708-3719.

Figures/Tables 9

Fig.1 Phase structure and microstructure of PBFT and PBFTN

Fig.2 Phase structure and microstructure of PBFT and PBFTN after reduction

Fig.3 TEM and EDX images of PBFTN after reduction in H2

Fig.4 Fe 2p XPS of samples before and after reduction and conductivities of PBFT and PBFTN in air

Fig.5 O 1s XPS of the PBFT and PBFTN and Ni 2p XPS of PBFTN before and after reduction

Table 1 Summary of Rietveld refinement results of XRD data for PBFT and PBFTN samples

材料	空间群	a/Å	b/Å	c/Å	V/Å³
合成的PBFT	P4/mmm	3.936795	3.936795	7.878303	122.101
合成的PBFTN	P4/mmm	3.928727	3.928727	7.866324	121.416
H₂还原后的PBFTN	P4/mmm	3.941746	3.941746	3.941746	122.980

Table 2 Fe4+/Fe3+/Fe2+ content in PBFT and PBFTN

材料	含量/%			平均价态
材料	Fe⁴⁺	Fe³⁺	Fe²⁺	平均价态
合成的PBFT	14.9	64.9	20.2	2.95
H₂还原后的PBFT	13.5	58.9	27.6	2.87
合成的PBFTN	20.0	64.5	15.5	3.05
H₂还原后的PBFTN	18.3	61.0	20.7	2.98

Table 3 XPS analysis of O 1s for PBFT and PBFTN

材料	O_lat.(Fitting area)	O_ads.(Fitting area)	[O_ads./(O_lat.+O_ads.)]/%
合成的PBFT	30708	41584	57.5
H₂还原后的PBFT	33947	34747	50.6
合成的PBFTN	32529	43477	57.2
H₂还原后的PBFTN	28598	46487	61.9

Fig.6 Electrochemical properties characterization of PBFT and PBFTN

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Investigation on PrBaFe₂O_6-_δ anode material with in-situ FeNi nanoparticle in direct carbon solid oxide fuel cell

原位析出纳米合金的PrBaFe₂O_6-_δ 基阳极构筑及其在固体碳燃料电池中的应用研究

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