硅酸盐学报

用负热膨胀氧化物Sm_0.85Zn_0.15MnO₃复合La_0.6Sr_0.4CoO_3-_δ材料制备中温固体氧化物燃料电池空气极

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司宇 ¹^,² , 高铭泽 ² , 李世清 ² , 官万兵 ² , 杨钧 ² , 王建新 ²

硅酸盐学报 | 研究论文 2024,52(12): 3772-3780

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硅酸盐学报 |研究论文 2024 , 52 (12) : 3772 -3780

用负热膨胀氧化物Sm_0.85Zn_0.15MnO₃复合La_0.6Sr_0.4CoO_3-_δ材料制备中温固体氧化物燃料电池空气极

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司宇¹^,², 高铭泽², 李世清², 官万兵², 杨钧², 王建新²

作者信息

^1．宁波大学材料科学与化学工程学院，浙江宁波 315211

^2．中国科学院宁波材料技术与工程研究所，浙江省先进燃料电池与电解池技术重点实验室，浙江宁波 315201

通讯作者:

王建新（1980—），男，博士，研究员。

作者简介:

司宇（1998—），男，硕士研究生。

Negative Thermal Expansion Oxide Sm_0.85Zn_0.15Mno₃ Composite of La_0.6Sr_0.4CoO_3-_δ Materials as Intermediate Temperature Solid Oxide Fuel Cells High-Performance Air Electrode

Yu SI¹^,², Mingze GAO², Shiqing LI², Wanbing GUAN², Jun YANG², Jianxin WANG²

Affiliations

^1.College of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, Zhejiang, China

^2.Zhejiang Provincial Key Laboratory of Advanced Fuel Cell and Electrolyzer Technology, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China

Corresponding Author:

WANG Jianxin (1980-), male, Ph.D., Professor. E-mail: jxwang@nimte.ac.cn

SI Yu (1998-), male, Master candidate. E-mail: siyu@nimte.ac.cn

出版时间: 2024-12-20 doi: 10.14062/j.issn.0454-5648.20240261

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摘要

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La_0.6Sr_0.4CoO_3-_δ（LSC）材料是现在固体氧化物燃料电池（SOFC）空气极材料的主流研究方向之一，有着极佳的电化学性能，而其最大的短处就是热膨胀系数过大。负热膨胀材料因为特定温度区间内会呈现出热收缩的特性而被命名，复合后在理论上可以显著降低材料的热膨胀系数，更容易使SOFC空气极材料与电解质材料实现热匹配。本工作以LSC材料为基体，选择负热膨胀特性较为突出的Sm_0.85Zn_0.15MnO₃（SZM）材料作为复合相，研究了复合料的电化学性能。通过固-液复合法合成了负热膨胀（NTE）氧化物SZM，将之与La_0.6Sr_0.4CoO_3-_δ（LSC）机械混合形成LSC-xSZM（x= 0~40%）系列复合空气极材料。XRD结果显示SZM与LSC二者化学相容性良好。热膨胀测试表明，SZM有着优秀的热补偿能力，x= 30%时，复合材料在室温至800 ℃的平均热膨胀系数为13×10^-6 K^-1，与阻隔层材料相近。LSC-30% SZM复合材料在800~550 ℃的面比电阻由LSC的0.012~1.240 Ω·cm²降至0.008~0.620 Ω·cm²，展现良好的界面接触。纽扣电池在750 ℃的功率密度为1 702 mW·cm^-2，而同温的纯相LSC为1 209 mW·cm^-2，实现41%的提升；同步的极化电阻R_p由0.65 Ω·cm²降至0.50 Ω·cm²。热循环和恒流放电的电压降幅均在1%以下，测试后的电池截面SEM照片均未发生分层现象。由于复合材料良好的热匹配，界面接触更好，最终实现电池的功率密度和稳定性的同时提升。

关键词

固体氧化物燃料电池 / 空气极 / 负热膨胀 / 材料复合 / 稳定性

Abstract

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Introduction

Solid oxide fuel cell (SOFC) is one of the strong competitors of energy technology. SOFC has the characteristics of wide fuel selection, less pollution emission, high safety, and low noise as an excellent energy conversion and utilization device. However, the existing commercial SOFC still has some problems like high working temperature and large attenuation rate due to the limitation of material performance, restricting the application. Among the components of SOFC, the performance of air pole material is a key factor affecting SOFC. LSC material is one of the main research directions of solid oxide fuel cells (SOFC) air polar materials with the superior electrochemical properties, but its major disadvantage is a great thermal expansion coefficient (TEC). The negative thermal expansion (NTE) material provides an effective way to reduce the TEC of the SOFC air pole material. NTE material is named because of the characteristics of thermal contraction in the specific temperature interval. Theoretically, it can reduce the TEC of composite material and facilitate the thermal match between SOFC air electrode material and electrolyte material. Some NTE materials are a perovskite structure with a higher conductivity than Gd_0.2Ce_0.8O_2-_δ (GDC) of fluorite structure. These advantages make the theoretical cell power density of NTE composite air electrode material above the GDC composite cathode In this paper, La_0.6Sr_0.4CoO_3-_δ (LSC) material was used as a matrix, Sm_0.85Zn_0.15MnO₃ (SZM) material with the superior negative thermal expansion characteristics was selected as a composite phase, and a series of LS-xSZM (x = 0-40%) materials were designed to achieve the thermal matching of composite materials.

Methods

LSC and SZM powders were synthesized by a solid-liquid composite method. First, the corresponding quality of acetate raw materials was accurately weighed according to the stoichiometric ratio, and then the appropriate citric acid (CA) was weighed as a complexing agent according to the total metal particle weight and citric acid (CA) amount of 5∶1. All the raw materials were mixed with an appropriate amount of deionized water and ground in a ball mill at a speed of 300 r/min for more than 12 h. The turbid liquid in the ball mill was taken out and placed in a beaker, and the precursor powder was obtained after drying in the oven at 250 ℃ for 6 h, and then the LSC powder was obtained via calcination in a muffle furnace at 950 ℃ for 2 h, and the SZM powder was obtained via calcination at 1 300 ℃ for 2 h. The two powders were mixed with ethanol and ground in the ball mill for 6 h. The cathode slurry was prepared by mixing powders, and then full cells and symmetrical cells were made by screen printing for subsequent tests.

Results and discussion

The X-ray diffraction patterns show that the SZM is chemically compatible with LSC. The thermal expansion test indicates that SZM has an excellent thermal offset ability, and the average thermal expansion coefficient of the composite material from room temperature to 800 ℃ at x of 30% is 13×10^-6 K^-1, which is similar to that of the barrier material. The area specific resistance of the LSC-30% SZM composite material at 800-500 ℃ decreases from 0.012-1.240 Ω·cm² in the case of LSC to 0.008-0.620 Ω·cm², indicating a good interfacial contact. The power density of the button cell at 750 ℃ is 1 702 mW·cm^-2, while the pure phase LSC at the same temperature is 1 209 mW·cm^-2, which is increased by 41%. The polarization resistance Rp reduces from 0.65 Ω·cm² to 0.50 Ω·cm². The voltage drop of thermal cycling and constant current discharge is below 1%. In the 200 h constant current discharge test at 300 mA·cm^-2, the voltage of the battery remains stable after the initial increase, and the whole process only reduces to 10 mV, which is decreased by 1.2%, showing a good long-term stability. No delamination occurs in the SEM images of the battery cross-section after the test. The comprehensive analysis of a better interfacial contact due to a good thermal matching of the composites ultimately achieves a simultaneous increase in the power density and stability of the cell.

Conclusions

A perovskite structural oxide material of Sm_0.85Zn_0.15MnO₃ (SZM) with negative thermal expansion characteristics was synthesized by a solid-liquid recombination method. The XRD analysis indicated that SZM was chemical compatible with LSC. The pure phase SZM had special thermal shrinkage characteristics, while the thermal expansion characteristics of the composite materials decreased. The TEC of the pure phase LSC was 20 ×10^-6 K^-1, while the TEC of the 30% SZM composite LSC was only 13×10^-6 K^-1. The ASR of the composite material at 750 ℃ decreased from 0.02 Ω·cm² to 0.013 Ω·cm², while that at 550 ℃ decreased from 1.2 Ω·cm² to 0.6 Ω·cm², having an excellent performance. The battery of LSC-30% SZM material was improved at 750 ℃ from 1 209 mW·cm^-2 of pure phase LSC to 1 702 mW·cm^-2 of LSC-30% SZM, which was increased by 41%. In the thermal cycle test, the variation of battery OCV was within 1%, and the voltage decay rate of long-term constant current discharge at 200 h was 1.2%. The microscopic section analysis indicated that there was little interface stratification phenomenon. LSC-30% SZM composite material had good long-term thermal stability and structural stability.

Key words

solid oxide fuel cell / air pole / negative thermal expansion / material composite / stability

引用本文

司宇, 高铭泽, 李世清, 官万兵, 杨钧, 王建新. 用负热膨胀氧化物Sm_0.85Zn_0.15MnO₃复合La_0.6Sr_0.4CoO_3-_δ材料制备中温固体氧化物燃料电池空气极. 硅酸盐学报, 2024 , 52 (12) : 3772 -3780 . DOI: 10.14062/j.issn.0454-5648.20240261

Yu SI, Mingze GAO, Shiqing LI, Wanbing GUAN, Jun YANG, Jianxin WANG. Negative Thermal Expansion Oxide Sm_0.85Zn_0.15Mno₃ Composite of La_0.6Sr_0.4CoO_3-_δ Materials as Intermediate Temperature Solid Oxide Fuel Cells High-Performance Air Electrode[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (12) : 3772 -3780 . DOI: 10.14062/j.issn.0454-5648.20240261

基金

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国家自然科学基金(22209191; 11932005; U20A20251)

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2024年第52卷第12期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240261

接收时间：2024-04-03
首发时间：2026-10-22
出版时间：2024-12-20

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收稿日期：2024-04-03
修回日期：2024-05-02

基金

国家自然科学基金(22209191; 11932005; U20A20251)

作者信息

^1．宁波大学材料科学与化学工程学院，浙江宁波 315211

^2．中国科学院宁波材料技术与工程研究所，浙江省先进燃料电池与电解池技术重点实验室，浙江宁波 315201

通讯作者:

王建新（1980—），男，博士，研究员。

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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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