中国科学院上海应用物理研究所团队近期Applied Catalysis B: Environment and Energy观点：实现用于高性能可逆固体氧化物电池的B位高熵空气电极
【Article Information】
Realization of a B-position high-entropy air electrode for high-performance reversible solid oxide batteries
First Author: Xia Ziting
Contact:ZHANG Linjuan*,WANG Jianqiang*,HU Zhiwei*
Affiliation: Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Max Planck Institute for Solid State Chemical Physics, University of Chinese Academy of Sciences, Singapore Science, Technology and Research Agency (A*STAR)
【Background】
With the increasing global energy demand and environmental protection pressure, reversible solid oxide batteries (R-SOCs) have attracted attention due to their low emissions, high efficiency, and strong fuel adaptability. However, the degradation of performance caused by electrode stripping and polarization limits its application, so there is a need to develop air electrode materials with high conductivity, excellent catalytic activity, and structural stability.
Cobalt-based biperovskite oxides based on perovskite structures have attracted much attention due to their rapid ionic diffusion and enhanced catalytic activity, but their lattice expansion at high temperatures and the cost of cobalt limit their applications. High-entropy perovskite oxides (HEPOs) reduce cobalt content, improve the matching of the coefficient of thermal expansion between the air electrode and the electrolyte, and improve the overall performance of the material by introducing multiple elements at the B site.
【Introduction】
近日，来自中科院上海应用物理研究所的张林娟、王建强研究员与德国马普所的胡志伟教授等合作，在国际知名期刊《Applied Catalysis B: Environment and Energy》上发表了题为“Realizing B-site high-entropy air electrode for superior reversible solid oxide cells”的研究论文。 该研究重点介绍了通过在B位引入高熵设计，制备了一种具有高催化活性和长寿命的单相空气电极材料PrBa0.8Ca0.2Fe0.4Co0.4Ni0.4Cu0.4Zn0.4O6-δ（HE-PBC-FCNCZ）。 该电极在700 ℃的燃料电池模式下展示了1.42 W cm-2的峰值功率密度，并且在长时间的稳定性测试中表现出极小的性能衰减。
The results show that the high-entropy design significantly improves the electrochemical performance and structural stability of the air electrode, reduces the amount of cobalt, enhances the matching of the thermal expansion coefficient with the electrolyte, and improves the overall performance of the material through multi-element synergy. X-ray absorption near-edge structure (XANES) analysis further confirmed that the material had minimal change in oxygen content during long-term operation, confirming its superior stability. This research provides a new idea and method for the development of high-performance and high-durability air electrodes for solid oxide batteries.
【Main points of the text】
Point 1: The introduction of high-entropy design
In this study, a high-entropy air electrode material HE-PBC-FCNCZ was successfully prepared by introducing a variety of elements (Fe, Co, Ni, Cu, Zn) at the B position. The high-entropy design significantly reduces the amount of cobalt used, thereby reducing material costs, while enhancing the matching of the coefficient of thermal expansion of the air electrode to the electrolyte. This multi-element synergy allows the material to maintain excellent electrochemical properties and structural stability at high temperatures.
Point 2: Excellent electrochemical performance
The HE-PBC-FCNCZ exhibits a peak power density of 1.42 W cm-2 in 700°C fuel cell mode, far exceeding the performance of traditional perovskite cathode materials. This high performance is due to the multi-element synergy of the high-entropy design, which allows the material to maintain excellent catalytic activity and ionic conductivity at high temperatures. The experimental results show that the conductivity of the material is significantly higher than that of the traditional material at different temperatures, reflecting its superior electrochemical performance.
Point 3: Excellent long-term stability
In stability tests of up to 500 hours, the HE-PBC-FCNCZ electrode exhibited minimal degradation of performance. X-ray absorption near-edge structure (XANES) analysis showed that the oxygen content of HE-PBC-FCNCZ changed the least after the stability test, indicating its superior structural stability. In addition, the material exhibited excellent stability in both fuel cell mode and electrolysis mode, maintaining good performance in 490 hours and 120 hours of testing, respectively.
Point 4: Structural advantages of high-entropy materials
The high-entropy design makes the HE-PBC-FCNCZ have a higher oxygen vacancy concentration and a more stable electrochemical environment. These oxygen vacancies help improve the ionic conductivity and catalytic activity of the material, while enhancing its structural integrity under complex operating conditions. The synergistic effect of multiple elements not only improves the thermodynamic properties of the electrode material, but also enhances its stability under high temperature and humidity conditions. The microstructure analysis showed that the particles of HE-PBC-FCNCZ were uniformly distributed and there was no obvious element aggregation.
Point 5: Wide application prospects
The excellent performance and long life of HE-PBC-FCNCZ material make it have a wide application prospect in reversible solid oxide batteries (R-SOCs). This study provides new ideas and methods for the development of high-performance and high-stability battery materials in the future. High-entropy designs are not only suitable for solid oxide batteries, but can also be generalized to other electrochemical energy storage and conversion devices, such as fuel cells and electrolyzers. The results show that high-entropy design is an effective material optimization strategy, which can significantly improve the comprehensive performance of electrode materials.
【Article Link】
Realizing B-site high-entropy air electrode for superior reversible solid oxide cells
https://doi.org/10.1016/j.apcatb.2024.124314
【About the Corresponding Author】
Linjuan Zhang, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Researcher, Doctoral Supervisor, Director of Energy Materials and Chemistry Research Department. National young talents, "outstanding members" of the Youth Innovation Promotion Association of the Chinese Academy of Sciences, high-level innovation and entrepreneurship and urgently needed talents in Jiading District, and high-level elite talents in Jiading District. His main research interests include electrocatalysis, in-situ electrochemical X-ray absorption spectroscopy and their applications. In J.Am.Chem.Soc. (cover), Nat.Commun. (Editor's Choice), Adv.Mater., Adv. Funct. Mater. et al. have published more than 100 SCI papers. He served as the fifth/sixth director of the Youth Innovation Promotion Association of the Chinese Academy of Sciences, the first director of the Actinide Physics and Chemistry Branch of the Chinese Nuclear Society, and the first director of the Actinide Physics and Chemistry Branch of the Chinese Nuclear Society. Member of the editorial board of Sci. Tech., Fundamental research, and The Innovation.
Jianqiang Wang, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Researcher, Doctoral Supervisor. He is a member of the Shanghai Institute of Applied Materials, Chinese Academy of Sciences, director of the Nuclear Energy Comprehensive Utilization Center, and director of the Inspection and Testing Center for Hydrogen Production Materials and Hydrogen Energy Products (CMA Certification). At Energy Environ. Sci., Angew Chem., J. Am. He has published more than 200 academic papers in Chem. Soc., and other journals. He has won the titles of Shanghai Advanced Worker, Outstanding Communist Party Member of the Chinese Academy of Sciences, Wang Kuancheng First Talent Program of the Chinese Academy of Sciences, Advanced Individual of Shanghai Science and Technology System, and Youth May Fourth Medal Collective of Shanghai Science and Technology System. At present, he is the vice chairman of the molten salt chemistry and technology branch of the Chinese Society for metals, the vice chairman of the Engineering Thermochemistry Professional Committee of the Chemical and Engineering Society of China, the vice chairman of the actinide physics and chemistry branch of the Chinese Nuclear Society, the member of the fuel cell professional committee of the China Energy Research Society, the green and low-carbon professional committee of the Chinese Energy Research Society, and the new energy professional committee member of the Chinese Petroleum Society.
胡志伟，德国马普固体化学物理研究所X射线光谱学组长。 主要采用同步辐射的波谱学方法，从理论与实验两方面研究凝聚态强关联体系中的电荷自旋、轨道态，开展有关磁性、超导性、多铁性, 新能源，环境，催化材料等方面的研究。 已在物理、材料等领域顶级期刊发表论文355篇，包括20篇Physical Review Letters (PRL)，14篇Nature Communications，多篇Proceedings of the National Academy of Sciences of the United States of America (PNAS)，Advanced Materials, J. Am. Chem. Soc., Angew. Chem. Int. Ed., Environ. Energy Science, joule论文等，为该领域的知名学者。
【Group Introduction】
The website of the research group https://www.x-mol.com/groups/hydrogen_energy
The team has been committed to the research of electrolyzed water for a long time, and has obtained more than 100 CMA certifications for inspection and testing capabilities, covering the comprehensive testing of key materials, single batteries, stacks and small systems, providing important technical support for enterprises and universities and institutes https://hydro.sinap.ac.cn/
With nearly 20 years of accumulation in the development of X-ray advanced spectroscopy technology, we have successively launched the desktop X-ray absorption spectrometer SuperXAFS series products, which provide users with experimental data comparable to synchrotron radiation XAFS with high-quality X-rays, excellent energy resolution and ultra-precise linkage scanning system.