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

作　　者：Xiaohui Li Li Yang Zhenyu Zhu Xiaoge Wang Pohua Chen Senchuan Huang Xianyi Wei Guohong Cai Pascal Manuel Sihai Yang Jianhua Lin Xiaojun Kuang Junliang Sun 李晓辉;杨利;朱振宇;王晓鸽;陈柏桦;黄森传;魏先益;蔡国鸿;Manuel Pascal;杨四海;林建华;匡小军;孙俊良(Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials,College of Chemistry and Bioengineering,Guilin University of Technology,Guilin 541004,China;College of Chemistry and Molecular Engineering,Peking University,Beijing National Laboratory for Molecular Science(BNLMS),Beijing 100871,China;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;MOE Key Laboratory of Bioinorganic and Synthetic Chemistry,School of Chemistry,Sun Yat-Sen University,Guangzhou 510275,China;ISIS Facility,Science and Technology Facilities Council(STFC),Rutherford Appleton Laboratory,Chilton,OX110QX,UK;Department of Chemistry,University of Manchester,Manchester M139PL,UK)

机构地区：[1]Guangxi Key Laboratory of Electrochemical and Magnetochemical Functional Materials,College of Chemistry and Bioengineering,Guilin University of Technology,Guilin 541004,China [2]College of Chemistry and Molecular Engineering,Peking University,Beijing National Laboratory for Molecular Science(BNLMS),Beijing 100871,China [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 [4]MOE Key Laboratory of Bioinorganic and Synthetic Chemistry,School of Chemistry,Sun Yat-Sen University,Guangzhou 510275,China [5]ISIS Facility,Science and Technology Facilities Council(STFC),Rutherford Appleton Laboratory,Chilton,OX110QX,UK [6]Department of Chemistry,University of Manchester,Manchester M139PL,UK

出　　处：《Science China Materials》2022年第10期2737-2745,共9页中国科学（材料科学（英文版）

基　　金：the National Natural Science Foundation of China(22090043 and 21622101);Guangxi Natural Science Foundation(2019GXNSFGA245006)for financial support;the National Natural Science Foundation of China(21527803 and 21621061);the Ministry of Science and Technology of China(2016YFA0301004)for financial support;the funding from China Postdoctoral Science Foundation(8206300392)。

摘　　要：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/GeO_(3)-based materials,and the considerable flexibility of BO_(n) polyhedra in terms of coordination number,rotation,deformation,and linkage,we report the first borate-base family of oxide ion conductors,(Gd/Y)_(1−x)Zn_(x)BO_(3−0.5x),through combined computational prediction and experimental verification.The oxygen vacancies in(Gd/Y)BO_(3)can be accommodated by forming B_(3)O_(8)units in isolated,3-fold,tetrahedral rings of B_(3)O_(9)and transported through a cooperative mechanism of oxygen exchange between the B_(3)O_(9)and B_(3)O_(8)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.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)O_(3)材料中刚性(Si/Ge)_(3)O_(9)基团无法容纳氧空位,以及BO_(n)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)-Zn_(x)BO_(3−0.5x).(Gd/Y)BO_(3)中的氧空位可以通过孤立的B_(3)O_(9)三元环形成B_(3)O_(8)结构单元来容纳,并通过B_(3)O_(9)和B_(3)O_(8)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.

关 键 词：solid oxide fuel cells (Gd/Y)1−xZnxBO3−0.5x oxide ion migration mechanism borate oxide ion conductors ab initio molecular dynamics simulations 

分 类 号：TQ128[化学工程—无机化工] TM911.4[电气工程—电力电子与电力传动]