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Imaging the diffusion pathway of Al3+ ion in NASICON-type (Al0.2Zr0.8)20/19Nb(PO4)3 as electrolyte for rechargeable solid-state Al batteries |
Jie Wang(王捷)1, Chun-Wen Sun(孙春文)1,6,9, Yu-Dong Gong(巩玉栋)1, Huai-Ruo Zhang(张怀若)2,3, Jose Antonio Alonso4, María Teresa Fernández-Díaz5, Zhong-Lin Wang(王中林)1,6,7,9, John B Goodenough8 |
1 CAS Center for Excellence in Nanoscience, Beijing Institute of Nanoenergy and Nanosystems, Chinese Academy of Sciences(CAS), Beijing 100083, China;
2 Theiss Research, La Jolla, California 92037, USA;
3 Material Measurement Laboratory, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, USA;
4 Instituto de Ciencia de Materiales de Madrid, CSIC, Cantoblanco 28049 Madrid, Spain;
5 Institut Laue Langevin, BP 156 X, GrenobleCedex, France;
6 School of Nanoscience and Technology, University of Chinese Academy of Sciences, Beijing 100049, China;
7 School of Material Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0245, USA;
8 Texas Materials Institute, The University of Texas at Austin, Austin, Texas 78712, USA;
9 Center on Nanoenergy Research, School of Physical Science and Technology, Guangxi University, Nanning 530004, China |
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Abstract Among all-solid-state batteries, rechargeable Al-ion batteries have attracted most attention because they involve three-electron-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)3 oxide is identified by temperature-dependent neutron powder diffraction and aberration-corrected scanning transmission electron microscopy experiments. (Al0.2Zr0.8)20/19Nb(PO4)3 shows a rhombohedral structure consisting of a framework of (Zr,Nb)O6 octahedra 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.
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Received: 26 September 2018
Revised: 21 October 2018
Accepted manuscript online:
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PACS:
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82.33.Pt
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(Solid state chemistry)
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82.45.Gj
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(Electrolytes)
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82.45.Xy
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(Ceramics in electrochemistry)
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Fund: Project supported by the National Natural Science Foundation of China (Grant Nos. 51672029, 51372271, and 51172275) and the National Key Research and Development Project from the Ministry of Science and Technology, China (Grant No. 2016YFA0202702). |
Corresponding Authors:
Chun-Wen Sun, Huai-Ruo Zhang, Jose Antonio Alonso
E-mail: sunchunwen@binn.cas.cn;huairuo.zhang@nist.gov;ja.alonso@icmm.csic.es
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Cite this article:
Jie Wang(王捷), Chun-Wen Sun(孙春文), Yu-Dong Gong(巩玉栋), Huai-Ruo Zhang(张怀若), Jose Antonio Alonso, María Teresa Fernández-Díaz, Zhong-Lin Wang(王中林), John B Goodenough Imaging the diffusion pathway of Al3+ ion in NASICON-type (Al0.2Zr0.8)20/19Nb(PO4)3 as electrolyte for rechargeable solid-state Al batteries 2018 Chin. Phys. B 27 128201
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