Sintering-induced cation displacement in protonic ceramics and way for its suppression

Ze Liu; Yufei Song; Xiaolu Xiong; Yuxuan Zhang; Jingzeng Cui; Jianqiu Zhu; Lili Li; Jing Zhou; Chuan Zhou; Zhiwei Hu; Guntae Kim; Francesco Ciucci; Zongping Shao; Jian-Qiang Wang; Linjuan Zhang

doi:10.1038/s41467-023-43725-x

Sintering-induced cation displacement in protonic ceramics and way for its suppression

Nat Commun. 2023 Dec 2;14(1):7984. doi: 10.1038/s41467-023-43725-x.

Authors

Ze Liu^{1

2}, Yufei Song³, Xiaolu Xiong¹, Yuxuan Zhang¹, Jingzeng Cui^{1

2}, Jianqiu Zhu^{1

2}, Lili Li⁴, Jing Zhou¹, Chuan Zhou⁵, Zhiwei Hu⁶, Guntae Kim¹, Francesco Ciucci⁷, Zongping Shao⁸, Jian-Qiang Wang^{9

10}, Linjuan Zhang^{11

12}

Affiliations

¹ Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China.
² University of Chinese Academy of Sciences, Beijing, 100049, China.
³ Department of Mechanical and Aerospace Engineering, The Hong Kong University of Science and Technology, Clear Water Bay, Hong Kong, China.
⁴ State Key Laboratory of Crystal Materials and Institute of Crystal Materials, Shandong University, Jinan, 250100, China.
⁵ State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing, 211816, China.
⁶ Max Planck Institute for Chemical Physics of Solids, Dresden, 01187, Germany.
⁷ Chair of Electrode Design for Electrochemical Energy Storage Systems, University of Bayreuth, Weiherstraße 26, Bayreuth, 95448, Germany.
⁸ WA School of Mines: Minerals, Energy and Chemical Engineering, Curtin University, Perth, WA6845, WA, Australia. zongping.shao@curtin.edu.au.
⁹ Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China. wangjianqiang@sinap.ac.cn.
¹⁰ University of Chinese Academy of Sciences, Beijing, 100049, China. wangjianqiang@sinap.ac.cn.
¹¹ Key Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai, 201800, China. zhanglinjuan@sinap.ac.cn.
¹² University of Chinese Academy of Sciences, Beijing, 100049, China. zhanglinjuan@sinap.ac.cn.

Abstract

Protonic ceramic fuel cells with high efficiency and low emissions exhibit high potential as next-generation sustainable energy systems. However, the practical proton conductivity of protonic ceramic electrolytes is still not satisfied due to poor membrane sintering. Here, we show that the dynamic displacement of Y³⁺ adversely affects the high-temperature membrane sintering of the benchmark protonic electrolyte BaZr_0.1Ce_0.7Y_0.1Yb_0.1O_3-δ, reducing its conductivity and stability. By introducing a molten salt approach, pre-doping of Y³⁺ into A-site is realized at reduced synthesis temperature, thus suppressing its further displacement during high-temperature sintering, consequently enhancing the membrane densification and improving the conductivity and stability. The anode-supported single cell exhibits a power density of 663 mW cm^-2 at 600 °C and long-term stability for over 2000 h with negligible performance degradation. This study sheds light on protonic membrane sintering while offering an alternative strategy for protonic ceramic fuel cells development.