Zhou Lijia, Xu Jungu, Allix Mathieu, Kuang Xiaojun
Guangxi Key Laboratory of Optical and Electronic Materials and Devices, College of Materials Science and Engineering, Guilin University of Technology, Guilin, 541004, P. R. China.
CNRS, CEMHTI UPR3079, Univ. Orléans, F-45071, Orléans, France.
Chem Rec. 2020 Oct;20(10):1117-1128. doi: 10.1002/tcr.202000069. Epub 2020 Jul 30.
Lowering the operating temperature of solid oxide fuel cells (SOFCs) requires high performance oxide ion conductor electrolytes. Recently tetrahedra-based structures have been attracting considerable attention for oxide ion conductor development, among which the layered tetrahedral network melilite structure appears particularly interesting owing to its remarkable capability to accommodate and transport interstitial oxide ions, compared with isolated tetrahedral anion structures. Stabilization and migration mechanisms of interstitial oxide ions in melilites have been systematically investigated using local structural relaxation from both electrostatic Coulomb interaction and chemical bonding aspects based on atomic and electronic structures respectively using experimental and theoretical approaches. These reveal cationic size and chemical bonding effects on stabilization and migration mechanisms of interstitial oxide ions. Lately, full crystallization from glass, an innovative synthesis method, was employed to produce new metastable melilite oxide ion conductors which are inaccessible using classic solid state reaction owing to cationic size effect. Finally, the thermal and chemical stability at low temperature and the high oxide ion conductivity of the best melilite oxide ion conductors based on LaSrGa O are likely to provide real possibilities of applications of melilite-type electrolytes in SOFCs and other related devices.
降低固体氧化物燃料电池(SOFC)的工作温度需要高性能的氧化物离子导体电解质。最近,基于四面体的结构在氧化物离子导体开发方面引起了相当大的关注,其中层状四面体网络钙黄长石结构因其与孤立四面体阴离子结构相比,具有显著的容纳和传输间隙氧化物离子的能力而显得尤为有趣。基于原子和电子结构,分别使用实验和理论方法,从静电库仑相互作用和化学键合两个方面,通过局部结构弛豫系统地研究了钙黄长石中间隙氧化物离子的稳定化和迁移机制。这些研究揭示了阳离子尺寸和化学键对间隙氧化物离子稳定化和迁移机制的影响。最近,一种创新的合成方法——从玻璃中完全结晶,被用于制备新的亚稳钙黄长石氧化物离子导体,由于阳离子尺寸效应,使用经典固态反应无法获得这些导体。最后,基于LaSrGaO的最佳钙黄长石氧化物离子导体在低温下的热稳定性和化学稳定性以及高氧化物离子电导率,可能为钙黄长石型电解质在SOFC和其他相关器件中的应用提供实际可能性。