硅酸盐学报

质子陶瓷电池氧电极材料设计及稳定性研究进展

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张晓玉 ¹ , 马丽丽 ² , 王睿 ² , 杨磊 ² , 刘魁 ¹ , 黄祖志 ³ , 陈婷 ¹ , 王绍荣 ¹

硅酸盐学报 | 综合评述 2024,52(7): 2442-2452

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硅酸盐学报 |综合评述 2024 , 52 (7) : 2442 -2452

质子陶瓷电池氧电极材料设计及稳定性研究进展

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张晓玉¹, 马丽丽², 王睿², 杨磊², 刘魁¹, 黄祖志³, 陈婷¹, 王绍荣¹

作者信息

^1．中国矿业大学，江苏徐州 221116

^2．中广核风电有限公司，北京 100070

^3．江西科技师范大学，南昌 330038

通讯作者:

王绍荣（1964—），男，博士，教授。

作者简介:

张晓玉（1988—），女，博士研究生。

Research Progress on Materials Design and Stability of Oxygen Electrode in Proton Ceramic Cells

Xiaoyu ZHANG¹, Lili MA², Rui WANG², Lei YANG², Kui LIU¹, Zuzhi HUANG³, Ting CHEN¹, Shaorong WANG¹

Affiliations

^1.China University of Mining and Technology, Xuzhou 221116, Jiangsu, China

^2.CGN Wind Power Co., LTD, Beijing 100070, China

^3.Jiangxi Science and Technology Normal University, Nanchang 330038, China

Corresponding Author:

WANG Shaorong (1964-), male, Ph.D., Professor. E-mail: srwang@cumt.edu.cn

ZHANG Xiaoyu (1988-), female, Doctoral candidate. E-mail: xiaoyucumt@163.com

出版时间: 2024-07-20 doi: 10.14062/j.issn.0454-5648.20230839

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摘要

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质子陶瓷电池（PCCs）可广泛用于发电、储能和可持续化学合成等研究领域，其工作温度适中、效率高，具有广阔的应用前景。然而，在中低温时，PCCs氧电极的氧析出反应（OER）和氧还原反应（ORR）动力学缓慢，材料稳定性差，导致其难以高效、稳定地运行。因此，设计和开发活性高、稳定性良好的氧电极对促进PCCs技术的发展至关重要。本工作探讨了PCCs氧电极的材料组分、结构与电化学性能之间的关系，重点阐述了影响氧电极材料稳定性的因素，分别讨论了电解质-氧电极界面，氧电极在高湿度、含CO₂气氛和含Cr气氛下的稳定性，以及抑制其衰减的策略，并就氧电极材料设计及未来发展方向进行了展望。

关键词

质子陶瓷电池 / 氧电极 / 材料设计 / 电化学性能 / 稳定性

Abstract

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Proton ceramic cells (PCCs) are widely investigated as devices for power generation, energy storage, and sustainable chemical synthesis because of their moderate operating temperature, high efficiency and great application prospects. Nevertheless, a main challenge for oxygen electrode of PCCs remains the sluggish kinetics of the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) at intermediate and lower temperatures as well as the insufficient stability of the oxygen electrode materials in the operating environment. Designing and developing high-performance and durable oxygen electrodes is thus crucial for promoting the industrial application of PCCs technology. This review discussed the relationships among composition, structure and electrochemical performance of oxygen electrode materials and summarized the factors that impact the stability of oxygen electrode. The stability of electrolyte and oxygen electrode interface under high steam condition, CO₂ atmosphere and Cr atmosphere was discussed. In addition, a future research in oxygen electrode stability was also proposed.

The elementary reactions at the oxygen electrode include oxygen adsorption and dissociation, charge/oxygen/proton transfer, as well as water formation and exhaust. It is considered that protons can play a critical role in the reaction process on the oxygen electrode in addition to electrons and oxygen ions based on the elementary reactions occurring on the oxygen electrode. Triple ion-electronic-protonic conducting (TIEC) materials can extend the triple-phase boundary (TPB) area to the entire surface of the oxygen electrode. Besides the basic requirements of high activity and electrochemical performance, the oxygen electrode also needs to have a sufficient porosity, a good stability, and a matched thermal expansion coefficient with the electrolyte.

Developing new materials or optimizing their compositions is a possible way to improve the intrinsic characteristics of materials. Effective design strategies include element doping (A/B/O-site doping) or the construction of A- and B-site defects. The A-site in the perovskite structure ensures a large lattice volume and prevents lattice distortion, and doping elements in the A-site with large radii is beneficial to ion transport. The acceptor doping on the B-site can increase the electron cloud density around the oxygen atoms, thereby facilitating proton absorption. Also, the oxygen-site doping is more complicated. The substitution of oxygen by elements with a lower valence state and a higher electronegativity can promote the migration rate of oxide ions and protons. However, electron conductivity and carrier concentration may decrease after anion doping. The realization of optimal TIEC in single-phase materials is a challenge. Composite electrodes with different functions exhibit synergistic effects and strong interactions at the nanoscale, thus garnering increasing attention. Composite oxygen electrode can improve the mismatched thermal mechanical issue between the oxygen electrode and the electrolyte, and enhance the chemical stability towards CO₂ and H₂O, thereby increasing the long-term stability of PCCs. Methods for preparing composite oxygen electrodes include mechanical mixing, impregnation, self-assembly, and dissolution. Among these methods, the last three can be used to fabricate nano-sized composite oxygen electrodes with a superior performance.

The stability of the oxygen electrode and the interface between the oxygen electrode and the electrolyte has a significant impact on the lifespan of the PCCs. The adhesion between the electrode and the electrolyte is strengthened via depositing an intermediate layer to enhance PCCs stability. Active material with a high coefficient of thermal expansion can be combined with a negative thermal expansion material to form a composite oxygen electrode, exhibiting a well-matched thermal expansion characteristic with the electrolyte, which is beneficial to the thermal cycling stability of the PCCs. In addition to interface stability between the electrode and electrolyte, the stability of the oxygen electrode material is also crucial. Most oxygen electrode materials contain Ba and Sr elements, which tend to enrich and segregate on the electrode surface, especially in atmospheres containing H₂O and CO₂. Water can promote element segregation, leading to the formation of secondary phases through reactions with impurities in air, which affects the catalytic activity of the electrode material. The stability of oxygen electrode materials can be significantly improved via doping, developing materials without alkali elements, and using composite oxygen electrodes. In addition, other pollutants (such as Cr, Si, B) may be generated in the stack, which also affects the stability. Furthermore, the oxygen electrode of PCCs is exposed to humidified air when operated in the electrolysis cell mode. However, there is a limited research on the poisoning of PCCs oxygen electrodes towards high steam and other elements (Cr, Si).

Summary and prospects

PCCs is a key technology for renewable energy conversion and storage. The degradation of oxygen electrode greatly increases the polarization resistance of the cell and causes obviously declined performance. It is thus urgent to improve the stability of oxygen electrode materials. A further research can be conducted in the following fields, i.e., the relationship between the composition and electrochemical performance of the oxygen electrode, the influence of microstructure evolution and morphology changes under a high humidity on electrochemical performance, and the corresponding degradation mechanisms; the thermal cycle stability and interface stability of oxygen electrode materials under actual operating conditions; the mechanism of the PCCs oxygen electrode poisoned by Cr and Si in a high humidified atmosphere, as well as corresponding detoxification strategies; and it is necessary for commercial application requirements to investigate the stability of large-area PCCs under typical operating conditions.

Key words

proton ceramic cells / oxygen electrode / materials design / electrochemical performance / stability

引用本文

张晓玉, 马丽丽, 王睿, 杨磊, 刘魁, 黄祖志, 陈婷, 王绍荣. 质子陶瓷电池氧电极材料设计及稳定性研究进展. 硅酸盐学报, 2024 , 52 (7) : 2442 -2452 . DOI: 10.14062/j.issn.0454-5648.20230839

Xiaoyu ZHANG, Lili MA, Rui WANG, Lei YANG, Kui LIU, Zuzhi HUANG, Ting CHEN, Shaorong WANG. Research Progress on Materials Design and Stability of Oxygen Electrode in Proton Ceramic Cells[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (7) : 2442 -2452 . DOI: 10.14062/j.issn.0454-5648.20230839

基金

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中央高校基本科研业务费专项资金资助(2023KYJD1010)
国家自然科学青年基金(52202334)
江苏省碳达峰碳中和科技创新专项资金(BK20220011)

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2024年第52卷第7期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230839

接收时间：2023-10-31
首发时间：2026-10-22
出版时间：2024-07-20

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收稿日期：2023-10-31
修回日期：2023-12-04

基金

中央高校基本科研业务费专项资金资助(2023KYJD1010)

国家自然科学青年基金(52202334)

江苏省碳达峰碳中和科技创新专项资金(BK20220011)

作者信息

^1．中国矿业大学，江苏徐州 221116

^2．中广核风电有限公司，北京 100070

^3．江西科技师范大学，南昌 330038

通讯作者:

王绍荣（1964—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230839

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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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