硅酸盐学报

可逆固体氧化物电池La_0.2Sr_0.8TiO_3-_δ基纤维燃料极的浸渍改性

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卢恺振 ¹^,³ , 王乐莹 ¹^,³ , 罗凌虹 ¹^,³ , 程亮 ²^,³ , 徐序 ¹^,³ , 吴也凡 ¹^,³

硅酸盐学报 | 研究论文 2024,52(5): 1676-1686

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硅酸盐学报 |研究论文 2024 , 52 (5) : 1676 -1686

可逆固体氧化物电池La_0.2Sr_0.8TiO_3-_δ基纤维燃料极的浸渍改性

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卢恺振¹^,³, 王乐莹¹^,³, 罗凌虹¹^,³, 程亮²^,³, 徐序¹^,³, 吴也凡¹^,³

作者信息

^1．景德镇陶瓷大学材料科学与工程学院，江西景德镇 333403

^2．景德镇陶瓷大学国家日用及建筑陶瓷工程技术中心，江西景德镇 333001

^3．景德镇陶瓷大学江西省燃料电池材料与器件重点实验室，江西景德镇 333001

通讯作者:

王乐莹（1988—），女，博士，讲师；

罗凌虹（1966—），女，博士，教授。

作者简介:

卢恺振（1996—），男，硕士研究生。

Impregnation Modification of La_0.2Sr_0.8TiO_3-δ-Based Fiber Fuel Electrode for Reversible Solid Oxide Cells

Kaizhen LU¹^,³, Leying WANG¹^,³, Linghong LUO¹^,³, Liang CHENG²^,³, Xu XU¹^,³, Yefan WU¹^,³

Affiliations

^1.School of Materials Science and Engineering, Jingdezhen Ceramic University, Jingdezhen 333403, Jiangxi, China

^2.National Engineering Research Center for Domestic & Building Ceramics Jingdezhen Ceramic University, Jingdezhen 333001, Jiangxi, China

^3.Jiangxi Provincial Key Laboratory of Fuel Cell Materials and Devices, Jingdezhen Ceramic University, Jingdezhen 333001, Jiangxi, China

Corresponding Author:

WANG Leying (1988-), female, Ph.D., Lecturer. E-mail: wly8858@163.com;

LUO Linghong (1966-), female, Ph.D., Professor. luolinghong@tsinghua.org.cn

LU Kaizhen (1996-), male, Master candidate. E-mail: jxjalkz@126.com

出版时间: 2024-05-20 doi: 10.14062/j.issn.0454-5648.20230630

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摘要

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开发适合可逆操作的高性能燃料极材料对可逆固体氧化物电池的发展至关重要。为解决La_xSr_1-_xTiO₃燃料极材料催化活性差及离子电导率低等问题，采用静电纺丝技术直接制备富含连通孔洞的La_0.2Sr_0.8TiO_3-_δ（LST）/氧化钇稳定型氧化锆（YSZ）复合纤维，构建了以LST骨架为电子通道主路、YSZ颗粒为离子通道穿插的三维网络混合导体通路，并通过浸渍Ce_0.9M_0.1O_2-_δ（M=Fe、Co、Ni）纳米颗粒对燃料极骨架修饰改性，增强燃料极与电解质层间的界面结合，研究不同浸渍物对纤维基燃料极催化活性的影响。结果表明：浸渍Ce_0.9Ni_0.1O_2-_δ的燃料极兼具有较强的氢氧化能力和氢还原能力，在浸渍物和Ni纳米颗粒析出的共同作用下，单电池在850 ℃、3%（体积分数）H₂O/H₂下的最高功率密度达到342 mW/cm²；在850 ℃、46.8%（体积分数）H₂O/H₂、1.3 V下的电解电流密度达到0.313 A/cm²。

关键词

可逆固体氧化物电池 / 燃料极 / 复合纤维 / 浸渍改性 / 弛豫时间分布

Abstract

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Introduction

The development of high-performance fuel electrode materials suitable for reversible operation is crucial for the application of reversible solid oxide cells (RSOCs). The fuel electrode should have excellent catalytic activity such as hydrogen oxidation reaction and hydrogen evolution reaction in the solid oxide fuel cells/solid oxide electrolysis cells (SOFC/SOEC) dual mode. Conventional Ni-YSZ fuel electrode materials are susceptible to sulfur poisoning when using fuel gas containing sulfur impurities and carbon buildup when using hydrocarbon fuel. La_xSr_1-_xTiO₃ perovskite materials have a superior resistance to coking and sulfur poisoning, which is widely used in RSOCs fuel electrodes in recent years. However, the poor ionic conduction and the non-ideal catalytic ability of fuel gas affect the further application of La_xSr_1-_xTiO₃ fuel electrodes. It is thus necessary for the improvement of the catalytic activity and the electrochemical performance of the fuel electrodes to optimize the microstructure and surface modification. In this paper, La_0.2Sr_0.8TiO_3-δ (LST)/YSZ-based fiber fuel electrode by Ce_0.9M_0.1O_2-δ (M=Fe,Co,Ni) impregnation modification was prepared, and the effect of impregnation on the electrochemical properties of fiber fuel electrode in SOFC/SOEC dual mode was investigated.

Methods

La_0.2Sr_0.8TiO_3-δ (LST)/YSZ composite fibers were directly prepared by an electrospinning method. In the preparation, stoichiometric amounts of La(NO₃)₃·6H₂O, Sr(NO₃)₂ and C₁₆H₃₆O₄Ti were weighed and dissolved with N, n-dimethylformamide (DMF) as a solvent and polyvinylpyrrolidone (PVP) as binder and one-dimensional template. The YSZ suspension was added to the LST precursor solution to obtain the LST/YSZ electrospinning solution for electrospinning. The high catalytic activity of Ce_0.9M_0.1O_2-δ (M=Fe, Co, Ni, CMO) was loaded on LST/YSZ composite fiber skeleton by an ion impregnation method to prepare the fiber fuel electrode. The electrolyte-supported single cells (CMO@LST/YSZ||YSZ||YSZ||GDC||LSCF/GDC) were fabricated to evaluate the electrochemical performance of the fiber fuel electrode.

The phase composition of the prepared composite fiber and the fuel electrode after immersion and calcination was determined by X-ray diffraction (XRD). The composite fiber morphology and the cross-section morphology of the tested fuel electrode were characterized by scanning electron microscopy (SEM). The two-phase distribution of the composite fiber was determined by high resolution transmission electron microscopy (HRTEM). The electrochemical performance of the fiber fuel electrodes in SOFC/SOEC dual-mode was tested via assembling a single cell. The impedance data were analyzed via the distribution of relaxation time (DRT), and the relationship between the microstructure and the electrochemical process was analyzed.

Results and discussion

The electrospinning solutions with stable spinning are prepared via adjusting the LST:YSZ mass ratio. The LST:YSZ with a mass ratio of 6∶4 shows a criss-cross fiber morphology and smooth surface with uniform diameters (i.e., 150-200 nm) through the electrospinning and calcination. The composite fibers consist of the LST skeleton with YSZ particles dispersed and embedded, which is prepared directly by electrospinning, thus forming a three-dimensional network of mixed conductor channels with electronic channels as the main path and ionic channels interspersed. The LST:YSZ composite fiber was used to prepare a fuel electrode skeleton, and CMO precursor solution is prepared to impregnate and modify the fuel electrode. Compared with the fiber morphology, the morphology of fiber fuel electrode is smaller in length and diameter, showing a short rod-like morphology. The surface of the fiber is evenly covered by the impregnated CMO nanoparticles (i.e., 50-80 nm), still retaining abundant and interconnected pores. The three-dimensional network fiber electrode is constructed. The impregnate uniformly wraps on the fiber surface to strengthen the interfacial bonding between the fuel electrode and the YSZ transitional layer.

The different impregnation modification has an effect on the catalytic activity of the fuel electrode in SOFC/SOEC dual mode. The fuel electrode using Ce_0.9Ni_0.1O_2-δ as an impregnate has more Ni nanoparticles exsolution after the testing, effectively increasing the length of the three-phase interface and the active sites for the catalytic reaction. Based on the comprehensive analysis of EIS and DRT, the modified fiber fuel electrode can significantly affect the interfacial charge transfer process corresponding to the middle- and low- frequency. Ni nanoparticles exsolution can adsorb/dissociate hydrogen, and have a tendency to form an activated complex with water molecules, so that the fiber fuel electrode has great hydrogen oxidation capacity and hydrogen reduction capacity.

Conclusions

LST/YSZ composite fiber with rich connected pores was directly prepared by an electrospinning technique. This fiber had a three-dimensional network hybrid conductor pathway with LST skeleton as the main electronic channel and YSZ particles as ion channel interspersed. The interface bond between the fuel electrode and the electrolyte layer was further enhanced via modifying the fuel electrode skeleton with CMO nanoparticles impregnation. The results showed that the fuel electrode with Ce_0.9Ni_0.1O_2-δ impregnation had a high hydrogen oxidation and reduction capacity. Under the combined action of the impregnation and the precipitation of Ni nanoparticles, the single cell had the maximum power density of 342 mW/cm² at 850 ℃, 3% (in volume fraction) H₂O/H₂, and the current density of 0.313 A/cm² under 46.8% H₂O/H₂ for electrolysis at 1.3 V.

Key words

reversible solid oxide cells / fuel electrode / composite fiber / impregnation modification / distribution of relaxation times

引用本文

卢恺振, 王乐莹, 罗凌虹, 程亮, 徐序, 吴也凡. 可逆固体氧化物电池La_0.2Sr_0.8TiO_3-_δ基纤维燃料极的浸渍改性. 硅酸盐学报, 2024 , 52 (5) : 1676 -1686 . DOI: 10.14062/j.issn.0454-5648.20230630

Kaizhen LU, Leying WANG, Linghong LUO, Liang CHENG, Xu XU, Yefan WU. Impregnation Modification of La_0.2Sr_0.8TiO_3-δ-Based Fiber Fuel Electrode for Reversible Solid Oxide Cells[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (5) : 1676 -1686 . DOI: 10.14062/j.issn.0454-5648.20230630

基金

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国家自然科学基金(51762026; 51802132)
江西省自然科学基金重点项目(20224ACB204010)
江西省教育厅科技落地计划(KJLD13072)
江西省教育厅科技项目(GJJ2201009; GJJ2201010)

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排序方式：

2024年第52卷第5期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230630

接收时间：2023-08-23
首发时间：2026-10-22
出版时间：2024-05-20

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出版历史

收稿日期：2023-08-23
修回日期：2023-10-17

基金

国家自然科学基金(51762026; 51802132)

江西省自然科学基金重点项目(20224ACB204010)

江西省教育厅科技落地计划(KJLD13072)

江西省教育厅科技项目(GJJ2201009; GJJ2201010)

作者信息

^1．景德镇陶瓷大学材料科学与工程学院，江西景德镇 333403

^2．景德镇陶瓷大学国家日用及建筑陶瓷工程技术中心，江西景德镇 333001

^3．景德镇陶瓷大学江西省燃料电池材料与器件重点实验室，江西景德镇 333001

通讯作者:

王乐莹（1988—），女，博士，讲师；

罗凌虹（1966—），女，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230630

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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