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Borates as a new direction in the design of oxide ion conductors

硼酸盐: 氧离子导体设计的一个新方向

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An Erratum to this article was published on 01 November 2022

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Abstract

Lowering the operating temperature of solid oxide fuel cells (SOFCs) has extensively stimulated the development of new oxide ion conductors. Here, inspired by the structural commonalities of oxide ion conductors, the inability to accommodate oxygen vacancies in the rigid, isolated, 3-fold tetrahedral rings of SrSi/GeO3-based materials, and the considerable flexibility of BOn polyhedra in terms of coordination number, rotation, deformation, and linkage, we report the first borate-base family of oxide ion conductors, (Gd/Y)1−xZnxBO3−0.5x, through combined computational prediction and experimental verification. The oxygen vacancies in (Gd/Y)BO3 can be accommodated by forming B3O8 units in isolated, 3-fold, tetrahedral rings of B3O9 and transported through a cooperative mechanism of oxygen exchange between the B3O9 and B3O8 units, which is assisted by the intermediate opening and extending of these units. This study opens a new scientific field of the borate system for designing and discovering oxide ion conductors.

摘要

降低固体氧化物燃料电池(SOFCs)的工作温度正在推动新型氧离子导体材料的开发. 在此, 受氧离子导体材料结构共性的启发, 基于Sr(Si/Ge)O3材料中刚性(Si/Ge)3O9基团无法容纳氧空位, 以及BOn 多面体在配位数、旋转、变形和连接上的巨大灵活性, 我们首次通过计算预测和实验验证, 报道了基于硼酸盐的新型氧离子导体材料(Gd/Y)1−x-ZnxBO3−0.5x. (Gd/Y)BO3 中的氧空位可以通过孤立的B3O9 三元环形成B3O8 结构单元来容纳, 并通过B3O9 和B3O8 单元之间的氧交换合作机制来传输, 而这些结构单元作为过渡态的打开和伸展则有助于氧的传输.这项研究为设计和开发新型氧离子导体开辟了新方向, 有望从硼酸盐家族发现更多新的氧离子导体.

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Acknowledgements

Kuang X thanks the National Natural Science Foundation of China (22090043 and 21622101) and Guangxi Natural Science Foundation (2019GXNSFGA245006) for financial support. Sun J thanks the National Natural Science Foundation of China (21527803 and 21621061) and the Ministry of Science and Technology of China (2016YFA0301004) for financial support. Li X acknowledges the funding from China Postdoctoral Science Foundation (8206300392). We thank STFC/ISIS for access to beamline WISH.

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  1. These authors contributed equally to this work.

Authors and Affiliations

  1. Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials, College of Chemistry and Bioengineering, Guilin University of Technology, Guilin, 541004, China

    Xiaohui Li  (李晓辉), Xianyi Wei  (魏先益) & Xiaojun Kuang  (匡小军)

  2. College of Chemistry and Molecular Engineering, Peking University, Beijing National Laboratory for Molecular Science (BNLMS), Beijing, 100871, China

    Xiaohui Li  (李晓辉), Zhenyu Zhu  (朱振宇), Xiaoge Wang  (王晓鸽), Pohua Chen  (陈柏桦), Guohong Cai  (蔡国鸿), Jianhua Lin  (林建华) & Junliang Sun  (孙俊良)

  3. MOE Key Laboratory of New Processing Technology for Nonferrous Metal and Materials, Guangxi Key Laboratory of Optical and Electronic Materials and Devices, Guangxi Universities Key Laboratory of Nonferrous Metal Oxide Electronic Functional Materials and Devices, College of Materials Science and Engineering, Guilin University of Technology, Guilin, 541004, China

    Li Yang  (杨利) & Xiaojun Kuang  (匡小军)

  4. MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou, 510275, China

    Senchuan Huang  (黄森传)

  5. ISIS Facility, Science and Technology Facilities Council (STFC), Rutherford Appleton Laboratory, Chilton, OX11 0QX, UK

    Pascal Manuel

  6. Department of Chemistry, University of Manchester, Manchester, M13 9PL, UK

    Sihai Yang  (杨四海)

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  1. Xiaohui Li  (李晓辉)
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Contributions

Li X carried out the syntheses and characterization of samples, as well as data analysis, and prepared the manuscript. Yang L performed the molecular dynamics simulations and oxygen vacancy formation energy calculations. Zhu Z performed the EMF measurements and provided the solid-state spectrum of the reference H3BO3. Wang X and Chen B performed the RED data collection. Huang S collected the energy spectra and TEM mapping data. Wei X and Cai G collected the variable temperature XRD data. Manuel P and Yang S helped collect the neutron diffraction data. Kuang X and Sun J conceived and supervised the project and revised the manuscript. All authors commented on the manuscript.

Corresponding authors

Correspondence to Xiaojun Kuang  (匡小军) or Junliang Sun  (孙俊良).

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Conflict of interest

The authors declare that they have no conflict of interest.

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Supporting data are available in the online version of the paper.

Xiaohui Li recieved his PhD degree from Sun Yat-Sen University in 2019. After finishing his postdoctoral work in Junliang Sun’s group at Peking University in 2021, he joined the Institute of Solid State Chemistry led by Xianran Xing at the University of Science and Technology Beijing. His research interests include the development of new oxide ion conductors, inorganic luminescence materials, and nitride dielectric materials.

Xiaojun Kuang received his BSc degree in chemistry from Nanchang University in 1999 and PhD degree in inorganic chemistry from Peking University in 2004. After post-doctoral trainning at the University of Liverpool and University of Durham, he was appointed as an associate professor at the School of Chemistry, Sun Yat-Sen University in 2010 before he settled down in Guilin in 2013. His current research interests include the discovery of new oxide ion conductors, oxide and (oxy)nitride dielectrics and their structure-property relationship.

Junliang Sun is a full professor at Peking University and the recipient of the National Science Foundation Distinguished Young Scholars Program. He received his BSc degree (2001) and PhD degree (2006) in chemistry from Peking University. After finishing his postdoctoral work at Cornell University and Stockholm University, he became an assistant professor at Stockholm University in 2009. In 2012, he moved to Peking University. His current research interests include the method development for structure determination, and synthesis and applications of porous materials and dense oxides.

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Li, X., Yang, L., Zhu, Z. et al. Borates as a new direction in the design of oxide ion conductors. Sci. China Mater. 65, 2737–2745 (2022). https://doi.org/10.1007/s40843-022-2044-3

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