Imaging the diffusion pathway of Al^3+ ion in NASICON-type (Al0.2Zr0.8)20/19Nb(PO4)3 as electrolyte for rechargeable solid-state Al batteries  

作　　者：Jie Wang Chun-Wen Sun Yu-Dong Gong Huai-Ruo Zhang 王捷;孙春文;巩玉栋;张怀若;Jose Antonio Alonso;María Teresa Fernández-Díaz;王中林;John B Goodenough

机构地区：[1]CAS Center for Excellence in Nanoscience, Beijing Institute of Nanoenergy and Nanosystems,Chinese Academy of Sciences (CAS) [2]School of Nanoscience and Technology, University of Chinese Academy of Sciences [3]Center on Nanoenergy Research, School of Physical Science and Technology, Guangxi University [4]Theiss Research [5]Material Measurement Laboratory, National Institute of Standards and Technology [6]Instituto de Ciencia de Materiales de Madrid, CSIC [7]Institut Laue Langevin [8]School of Material Science and Engineering, Georgia Institute of Technology [9]Texas Materials Institute, The University of Texas at Austin

出　　处：《Chinese Physics B》2018年第12期532-537,共6页中国物理B（英文版）

基　　金：Project supported by the National Natural Science Foundation of China(Grant Nos.51672029,51372271,and 51172275);the National Key Research and Development Project from the Ministry of Science and Technology,China(Grant No.2016YFA0202702)

摘　　要：Among all-solid-state batteries, rechargeable Al-ion batteries have attracted most attention because they involve threeelectron-redox reactions with high theoretic specific capacity. However, the solid Al-ion conductor electrolytes are less studied. Here, the microscopic path of Al3+-ion conduction of NASICON-type(Al0.2Zr0.8)20/19Nb(PO4)3oxide is identified by temperature-dependent neutron powder diffraction and aberration-corrected scanning transmission electron microscopy experiments.(Al0.2Zr0.8)20/19Nb(PO4)3shows a rhombohedral structure consisting of a framework of(Zr,Nb)O6octahedra sharing corners with(PO4) tetrahedra; the Al occupy trigonal antiprisms exhibiting extremely large displacement factors. This suggests a strong displacement of Al ions along the c axis of the unit cell as they diffuse across the structure by a vacancy mechanism. Negative thermal expansion behavior is also identified along a and b axes, due to folding of the framework as temperature increases.Among all-solid-state batteries, rechargeable Al-ion batteries have attracted most attention because they involve threeelectron-redox reactions with high theoretic specific capacity. However, the solid Al-ion conductor electrolytes are less studied. Here, the microscopic path of Al^(3+)-ion conduction of NASICON-type(Al_(0.2)Zr_(0.8))_(20/19)Nb(PO_4)_3 oxide is identified by temperature-dependent neutron powder diffraction and aberration-corrected scanning transmission electron microscopy experiments.(Al_(0.2) Zr_(0.8))_(20/19) Nb(PO_4)_3 shows a rhombohedral structure consisting of a framework of(Zr,Nb)O_6 octahedra sharing corners with(PO_4) tetrahedra; the Al occupy trigonal antiprisms exhibiting extremely large displacement factors. This suggests a strong displacement of Al ions along the c axis of the unit cell as they diffuse across the structure by a vacancy mechanism. Negative thermal expansion behavior is also identified along a and b axes, due to folding of the framework as temperature increases.

关 键 词：aluminum–ion battery solid electrolyte diffusion pathway negative thermal expansion 

分 类 号：O4[理学—物理]